Effect of membrane pretreatment on performance of solvent resistant nanofiltration membranes in methanol solutions

This paper reports the effect of membrane pretreatment using different organic solvents on the performance of polyamide, polyimide and polydimethylsiloxane (PDMS) membranes in methanol solutions. Membrane pretreatment using acetone, methanol and toluene results in significant changes of membrane flux and rejection for polyamide- and polyimide-based membranes (Desal-DK and STARMEM 228) due to membrane swelling. The Performance of a polydimethylsiloxane (PDMS)-based membrane (MPF-50) in methanol solutions was not significantly affected by membrane pretreatment.     

纳滤膜分离技术的应用进展

纳滤膜是一崭新的分离膜,本文综述了纳滤膜技术在食品、化工、饮用水、废水处理等领域的应用进展.并简单介绍了纳滤膜在有机溶剂中的应用研究.     

高分子纳滤膜的制备技术

纳滤膜是介入于反渗透膜和超滤膜之间的一种压力驱动的新型分离膜,已成为近年来研究的热点,由于其载留分子量范围相对较窄（200－1000）且孔径处于纳米级（10^-9m),因此膜材质的选择及制备技术成为制备出高性能纳滤膜的关键。本文介绍了高分子纳滤膜的几种主要的制备工艺,并概述了近年来国内外在高分子纳滤膜材质、制备方法以及所制膜性能及应用方面的研究进展。     

Nanofiltration of biogenic amines in acidic conditions: Influence of operation variables and modeling

Biogenic amines are present in some fermented and non-fermented beverages and can cause diseases. This study analyzes the feasibility of separating biogenic amines by nanofiltration in acidic medium. Solutions of chloride salts of three biogenic amines: putrescine, histamine and tyramine were filtered through a nanofiltration membrane with a 1000 Da molecular weight cut-off (MWCO) and a positive electrical charge at pH 3. Increasing the transmembrane pressure or cross flow velocity led to an increase in solute rejection and permeate flow. Moreover, a higher electrical charge or lower concentration of amine cations caused a larger rejection indicating that membrane-solutes repulsion governs the filtration process. Finally, the experimental results were analyzed using the classic Donnan–Steric pore model. Values of 0.83 nm and 5.4 μm were estimated for pore radius and membrane effective ratio thickness-porosity from the filtration of neutral solutes. Membrane volumetric charge density and the proton diffusivity inside the pores were estimated from the experimental results.     

Solvent flux through dense polymeric nanofiltration membranes

This work examines the flux performance of organic solvents through a polydimethylsiloxane (PDMS) composite membrane. A selection of n-alkanes, i-alkanes and cyclic compounds were studied in deadend permeation experiments at pressures up to 900 kPa to give fluxes for pure solvents and mixtures between 10 and 100 l m⁻² h⁻¹. Results for the chosen alkanes and aromatics, and subsequent modelling using the Hagen–Poiseuille equation, suggest that solvent transport through PDMS can be successfully interpreted via a predominantly hydraulic mechanism. It is suggested that the mechanism has a greater influence at higher pressures and the modus operandi is supported by the non-separation of binary solvent mixtures and a dependency on viscosity and membrane thickness. The effects of swelling that follow solvent–membrane interactions show that the relative magnitudes of the Hildebrand solubility parameter for the active membrane layer and the solvent(s) are a good indicator of permeation level. Solvents constituting a group (e.g. all n-alkanes) induced similar flux behaviours when corrections were made for viscosity and affected comparable swelling properties in the PDMS membrane layer.     

Separate and Concentrate Lactic Acid Using Combination of Nanofiltration and Reverse Osmosis Membranes

The processes of lactic acid production include two key stages, which are (a) fermentation and (b) product recovery. In this study, free cell of Bifidobacterium longum was used to produce lactic acid from cheese whey. The produced lactic acid was then separated and purified from the fermentation broth using combination of nanofiltration and reverse osmosis membranes. Nanofiltration membrane with a molecular weight cutoff of 100–400 Da was used to separate lactic acid from lactose and cells in the cheese whey fermentation broth in the first step. The obtained permeate from the above nanofiltration is mainly composed of lactic acid and water, which was then concentrated with a reverse osmosis membrane in the second step. Among the tested nanofiltration membranes, HL membrane from GE Osmonics has the highest lactose retention (97 ± 1%). In the reverse osmosis process, the ADF membrane could retain 100% of lactic acid to obtain permeate with water only. The effect of membrane and pressure on permeate flux and retention of lactose/lactic acid was also reported in this paper.     

Electrochemical behaviour of p-Si in methanol solutions of chlorides

The mechanism of anodic dissolutions of p-Si single crystals in CH₃OH–LiCl and CH₃OH–LiCl–HCl solutions was investigated by means of the following electrochemical methods: linear sweep voltammetry, the potentiostatic transient technique and XPS surface analysis. The dissolution of p-Si proceeds by a two-step mechanism with the creation of a Si(II) surface intermediate. At low anodic overvoltage the dissolution proceeds with the formation of porous silicon, probably through the reaction: 2Si(II)Si+Si(IV). Structural etching of the single crystals surface was observed at high anodic overvoltage (E>2 V). At this potential range, silicon dissolves with the formation of a Si(IV) soluble product. Electrolysis of the methanol solvent containing Si(IV) in the cell p-Si|CH₃OH–LiCl–Si(IV)|M, where M=Pt, Cu or 18/8 stainless steel, leads to the deposition of an amorphous organosilicon layer on the cathode. The analysis of the deposit performed by means of XPS, FTIR and SEM allows determination of the morphology and composition of the film. The layer consists of Si–OCH₃ compounds and can be created only in methanol solvent. The film is unstable in a humid atmosphere and undergoes transformation into a Si–OH layer.Contribution to the 3rd Baltic Conference on Electrochemistry, Gdansk-Sobieszewo, Poland, 23–26 April 2003Dedicated to the memory of Harry B. Mark, Jr. (28 February 1934–3 March 2003)     

EXAFS studies on the methanol and ethanol solutions of cobalt(II) bromides

The results of an EXAFS investigation of methanol and ethanol solutions of CoBr₂ are reported. The curve fitting analysis gives the coordination numbers and the Co–Br and Co-solvent distances. The results for both 0.2M and 3.8M CoBr₂ in ethanol show the existence of [CoBr₂(C₂H₅OH)₂] as the dominant species, although a considerable amount of octahedral species also exists in the solutions. In 0.2 and 3.3M CoBr₂ methanol solutions, the dominant species are [Co(CH₃OH)₆]²⁺ and [CoBr(CH₃OH)₅]⁺, respectively.     

Crosslinked integrally skinned asymmetric polyaniline membranes for use in organic solvents

Solvent stable integrally skinned asymmetric nanofiltration membranes were prepared from polyaniline. These membranes were made by phase inversion and then crosslinked using two different chemical crosslinkers, α,α′-dichloro-p-xylene and glutaraldehyde. The resultant membranes were found to be stable in various organic solvents including acetone, methanol, ethyl acetate, tetrahydrofuran and N,N-dimethyl formamide. Nanofiltration experiments carried out in acetone and dimethyl formamide showed that the membranes gave stable permeate fluxes and good separation performances in the nanofiltration range. Molecular weight cut-off (MWCO) of the membranes was found to be between 150 and 250 g mol⁻¹. These membranes were also found to be stable for operations at elevated temperatures up to 70 °C and possibly higher. Furthermore, no fillers or preservative agents are required to maintain the membranes in a dry state thereby increasing the ease of handling.     

Nanoporous asymmetric polyaniline films for filtration of organic solvents

A new family of functional materials is reported for organic solvent nanofiltration, with excellent chemical stability and high retention of solute molecules. Integrally skinned asymmetric polyaniline (PANI) membranes were fabricated from concentrated solutions of doped PANI by phase inversion. Doped PANI solutions were prepared by adding organic acids directly to PANI dissolved in a mixture of NMP and 4-methyl piperidine before casting. Among the organic acids investigated, maleic acid, phthalic acid, sulfosalicylic acid and camphorsulfonic acid were able to dope PANI without causing gelation. These acids acted as soft templates, creating nanoporosity in the thin skin layer of the asymmetric PANI film. Their removal by alkaline extraction created membranes through which small solvent molecules can pass. After extracting the organic acids, the membranes were thermally crosslinked which conferred excellent solvent stability. These membranes had a molecular weight cut-off (MWCO) in the range of 150–250 g mol⁻¹ in methanol, making them the tightest OSN membranes reported to date. It was found that an increase in crosslinking temperature or time led to a decrease in solvent flux. PANI membranes were found to be resistant to a variety of organic solvents such as ethyl acetate, acetonitrile and acetone. These remarkable membranes have the potential to be used in OSN operations at high temperatures (up to 150 °C), and gave increasing fluxes with increasing temperature while maintaining a high solute rejection.     

Relation between membrane characteristics and performance in nanofiltration

The performance of commercial membranes during nanofiltration of aqueous solutions containing dissolved uncharged or charged organic components, was studied on the basis of membrane characteristics by means of multiple linear regression.

The membrane characteristics studied were surface hydrophobicity, surface roughness, surface charge, molecular weight cut-off (MWCO), permeability and porosity of the top layer (expressed as the volume fraction of small and large pores, determined by Positron Annihilation Lifetime Spectroscopy). Filtration and adsorption experiments were performed in the presence of various components, which differ in molecular mass, hydrophobicity and (in the case of charged organic components) in charge.

It was concluded that in order to minimize fouling, the membrane should have a low volume fraction of small pores in the top layer. When the organic components are charged, a membrane with a large surface charge and a high hydrophilicity is also favourable. Not only the membrane, but also the feed characteristics have an influence on fouling: the best results during nanofiltration of dissolved uncharged or charged components were obtained with hydrophilic or negatively charged components, respectively. Dissolved organic components were the best retained by membranes with a low MWCO. In addition, uncharged organic components should be hydrophilic and small to obtain a high retention and minimal flux decline, while the interplay between membrane and component charge is crucial during filtration of dissolved charged organic components.     

Solvent-induced swelling of membranes — Measurements and influence in nanofiltration

This paper describes improvements to an apparatus for in-situ determinations of swelling where a linear inductive probe and electronic column gauge with an overall resolution of 0.1 μm was used for measurements of seven variants of polyacrylonitrile (PAN)/polydimethylsiloxane (PDMS) composite nanofiltration membranes in a range of alkane, aromatic and alcohol solvents. The unswollen membranes incorporated PDMS layers between 1 and 10 μm nominal thickness and were manufactured with a radiation and/or thermal crosslinking step.

The tested membranes exhibited a range of swelling dependent on the degree of crosslinking, the initial PDMS layer thickness and the type of solvent. With no applied pressure the PDMS layer on some radiation cross-linked membranes swelled as much as 170% of the initial thickness whilst other membranes were restricted to a maximum swelling of 80%. When a pressure up to 2000 kPa was applied to a membrane then swelling could be reduced to 20% of the value obtained at zero applied pressure. By vertically stacking up to three membrane samples it was possible to determine the swelling of PDMS layers as thin as 1 μm, although higher imposed pressures rendered some results unreliable as the measurement resolution of the apparatus was approached. The results of the swelling experiments are contrasted with crossflow nanofiltration performance in terms of solvent flux and solute rejection.     

纳滤膜在水处理中的最新应用进展

纳滤膜(NF)是新的分离膜品种,对溶质的截留性能介于超滤膜(UF)和反渗透膜(RO)之间。纳滤膜的特性是表面带有电荷并具有纳米级的微孔,能够去除高价离子和分子量大于200的溶解性的有机物。特殊的分离效果使纳滤技术单独或者和其它技术联用应用于水处理领域,主要包括:(1)饮用水制备和深度净化;(2)海水淡化;(3)废水处理,例如生活污水、垃圾渗滤液等等。本文综述了纳滤技术在上述水处理领域中的应用进展及现存问题。     

Electrochemical oxidation of organic pollutants in low conductive solutions

This mini-review supplies current opinion about the most recent works, which have been carried out toward the electrochemical treatment of organic compounds spike in low conductive solution. In particular, the first section is focused on the use of a solid polymer electrolyte in order to allow current flux with a low cell voltage even in a solution without supporting electrolyte. Meanwhile, the second section describes the microfluidic cells that are characterized by very small distances between electrodes (tens or few hundreds μm) that reduce the ohmic resistances and increase the mass transport of the pollutants to electrodes’ surfaces.     

Recovery of organic acids from waste salt solutions derived from the manufacture of cyclohexanone by electrodialysis

The possibility of recovery of organic acids from waste salt solution, derived from the manufacture of cyclohexanone, by means of single anion-exchange membrane electrodialysis was studied in this paper. Some key parameters, such as voltage, current density, pH value, current efficiency and specific energy consumption are studied and analyzed in details on theoretical basis. Results indicate that single anion-exchange membrane electrodialysis is found to be a feasible method for recovery of organic acids. Several valuable acids, such as butyric and adipic acids are effectively separated from waste salt solution by only one-step electrodialysis. And it consumes less energy compared to the conventional processes.     

Enhanced heavy oil recovery by organic alkali combinational flooding solutions

Although alkaline/surfactant/polymer (ASP) flooding is successfully applied in oil fields, some disadvantages such as scales, corrosion effects, and viscosity reductions of polymer solutions appear. Usage of organic alkalis can avoid or decrease these disadvantages. In this paper, the physicochemical properties, including interfacial tension (IFT), and viscosity, of organic alkali combinational flooding solutions and their effectiveness as enhanced oil recovery agents are investigated. Monoethanolamine (MEA) is the optimal one for decreasing the IFT among the three organic alkalis studied in this paper. Although MEA cannot decrease the IFT as low as NaOH does, it has good compatibility with both surfactant and the polymer hydrolyzed polyacrylamide (HPAM). MEA not only helps a surfactant solution or HPAM/surfactant mixture attain ultralow IFT values, but can also promote better viscosity stability for HPAM or HPAM/surfactant solutions compared to NaOH. Moreover, core flood experiments show that adding MEA can obtain additional tertiary oil recovery of 6%–10% original oil in place (OOIP) on the top of HPAM or HPAM/surfactant flooding, although MEA has a lower enhanced oil recovery than NaOH. The experimental results show that MEA is a good choice to replace NaOH in enhancing heavy oil recovery.     

Enhancing the performance of TFC nanofiltration membranes by adding organic acids in polysulfone support layer

Throughout this study, the effect of certain organic acids, methacrylic acid, lactic acid and tartaric acid, doped in polysulfone (PSF) casting solution onto the performance of nanofiltration (NF) membranes was investigated. Different NF membranes have been prepared from m-phenylenediamine and trimesoylchloride onto the top surface of the acid-modified PSF membranes through regulating the concentration and contact time of the conventional interfacial polymerization process. The study of scanning electron microscopy (SEM) was used to investigate the influence of acids on the morphology of membranes and cross-sectional structures. The functional groups, hydroxyl and carboxylic acid, of the acids have resulted in a significant increase in membrane thickness, porosity and hydrophilicity, with a decrease in macrovoid capacity of the PSF layer. The acid-modified PSF/TFC membranes showed higher rejection of salt, with an increment in water flux compared to the neat membrane. Water flux and salt rejection (R_s %) of the control membrane was 7.6 L/m² h and 65.4%, whereas polysulfone/methacrylic acid (PSF/MAAc), polysulfone/tartaric acid (PSF/TAc), and polysulfone/lactic acid (PSF/LAc) were 16.8, 18.5, and 20.2 L/m² h and 88, 88.2 and 94.1%, respectively. Efficiency of prepared NF membranes under various inlet pressures and specific salts was investigated with selectivity and salt rejection. The salt rejection of a mixed salt solution was found to meet the order of R_s % CaSO₄ ≥ R_s % Na₂SO₄ ˃ R_s % MgSO₄ ˃ R_s MgCl₂ ˃ Rs % NaCl.     

纳滤膜分离技术分离纯化多肽和氨基酸

综述了近十年来纳滤膜技术在氨基酸和多肽分离与纯化方面的研究进展。多肽和氨基酸的纳滤分离过程受溶液物化性质、氨基酸和多肽分子尺寸、所带电荷以及膜孔径、膜带电状态等多种因素的影响,建立该过程的分离机理模型、组合并优化分离条件是当前研究的热点。     

A batch membrane reactor for laboratory studies

A membrane reactor consisting of two recirculating flow systems connected via a membrane module has been constructed and used to study the dehydrogenation of cyclohexane. When the reactor is operated differentially it is possible to obtain the same information that is generated when using more conventional steady flow reactors. The batch system has the advantages of easily varying the ratio of membrane area to reactor volume and sampling a very wide range of effective Damköhler numbers. These are important variables in design studies. This ability has been demonstrated for the dehydrogenation of cyclohexane. The batch system reproduced results from studies using a more conventional flow reactor. In addition, with the batch reactor it was possible to experimentally confirm predictions that were based upon computer simulation but which were outside the range of experimental study for the conventional reactors used.     

Surface modification of nanofiltration membranes to improve the removal of organic micro-pollutants (EDCs and PhACs) in drinking water treatment: Graft polymerization and cross-linking followed by functional group substitution

A commercially available thin film composite (TFC) polyamide (PA) nanofiltration (NF) membrane was chemically modified to improve its rejection capacity for selected organic micro-pollutants categorized as endocrine disrupting chemicals (EDCs) and pharmaceutically active compounds (PhACs): bisphenol-A (BPA), ibuprofen, and salicylic acid. The raw NF membrane was altered using the following modification sequence: graft polymerization (methacrylic acid (MA)-membrane); cross-linking of grafted polymer chains (ethylene diamine (ED)-membrane); and, substitution of functional groups (succinic acid (SA)-membrane). Attenuated total reflective Fourier transform infrared (ATR-FTIR) was used to verify each modification in the sequence: the formation of amide bonds; graft polymerization and cross-linking; and, increased carboxylic acids on the modified membrane. Based on zeta-potential and contact angle measurements, graft polymerization increased the negative charge and hydrophilicity of the raw membrane, while cross-linking replaced carboxylic acid with amide bonds, which made the modified membrane almost neutral at pH 6.5. The water fluxes of the ED- and SA-membranes were similar to that of the raw membrane; however, the water flux of the MA-membranes varied with polymerization time (the membrane polymerized for 15 min revealed ≥20% higher flux than the raw membrane). BPA rejection by the raw membrane was substantially improved from 74% to ≥95% after this series of modifications. However, the rejection capacity of the ED-membrane for ibuprofen and salicylic acid was slightly reduced compared with those of the MA-membrane, which was polymerized for 15 min, due to the lack of an electrical repulsion mechanism. The SA-membrane recovered its negative surface charge and showed a clear enhancement in the rejection of all pollutants.