Optimum cleaning-in-place conditions for stainless steel microfiltration membrane fouled by terephthalic acid solids

Terephthalic acid (TPA) is a raw material of polyester fiber and polyethylene terephthalate. When TPA is produced by catalytic air oxidation of p-xylene in the presence of acetic acid solvent, most of produced TPA exists in the form of crystalline suspended solids. A microfiltration process may be used to recover TPA, but the microfilters are subjected to fouling and therefore cleaning-in-place (CIP) regimes need to be developed. In this research, the effects of variations to CIP conditions were investigated on the flux recovery accomplished in a TiO₂-sintered stainless steel microfiltration membrane (0.1 μm pore size) fouled with TPA. The extent of flux recovery was estimated as the ratio of the stabilized flux obtained during CIP to the water flux value achieved under corresponding operational conditions. Based upon batch solubility tests, sodium hydroxide (NaOH) was chosen as the major cleaning agent for the present experiment. The extent of flux recovery increased with increasing NaOH concentration over the range of 3–4% (w/v) NaOH, but decreased at NaOH concentrations above 4%. The flux recovery was favored at high cross-flow velocities, high temperatures and low transmembrane pressures. A high temperature run of cleaning did not produce any adverse effects up to 70 °C. The addition of surfactants (SDS and Tween 80) to the caustic cleaning agent led to a significant reduction in cleaning efficiency.     

Effect of Contamination and Cleaning of a Microfiltration Membrane in Filtration of an Aqueous Extract of Dog-Rose

The main factors responsible for decrease in the filtration flux (membrane throughput) in removal of pectin substances from an aqueous extract from dog-rose fruits and reasons for membrane contamination were studied. The method for membrane cleaning with distilled water and additional cleaning agents, aqueous solutions of NaOH and HNO₃, was optimized.     

Novel capsule phase microextraction in combination with high performance liquid chromatography with diode array detection for rapid monitoring of sulfonamide drugs in milk

Capsule phase microextraction is introduced herein for the first time to determine four sulfonamide residues in milk samples (sulfanilamide, sulfadiazine, sulfamethizole, and sulfathiazole). The technique eloquently integrates filtration and stirring mechanism into the extraction device, as such no filtration of the sample is needed prior to introducing the extraction device into the sample, and when placed on a magnetic stirrer, the device spins itself in order to diffuse the sample, resulting in faster extraction equilibrium. Microextraction capsules consist of three main parts; a magnet, a cellulose fiber substrate coated with high performance sol‐gel hybrid organic‐inorganic sorbent, and a porous membrane. Various encapsulated sol‐gel sorbents were tested in standard solutions prepared in deionized water and milk samples under different operational conditions. Analyte extraction time and elution time, type of sol‐gel sorbent, elution solvent, as well as the ratio of the sorbent to the elution solvent were among the optimized conditions. The protocols that yielded the best absolute recovery rates were subsequently tested in various milk samples. Method validation was performed in terms of linearity, accuracy and precision, reusability and ruggedness using the Youden test. The examined sulfonamides were subsequently analysed by reversed phase high performance liquid chromatography with diode array detection.     

Study on preparation and performances of cellulose acetate forward osmosis membrane

Cellulose acetate (CA) forward osmosis (FO) membranes were prepared via a phase inversion process. CA was used as membrane material for FO. Acetone and 1,4-dioxane were employed as solvent. Polyvinylpyrrolidone (PVP), maleic acid, and methanol were applied as additives. An orthogonal experiment was performed to optimize the ratio of every component in the casting solution. The membrane with best performance was selected to concentrate an anthocyanin solution. Saturated sucrose solution (about 60°Brix) was fit for using as draw solution in the concentration experiment. Water flux, porosity, and rejection rate were measured to evaluate the membrane properties. Reverse water rinsing was used in cleaning membrane that was fouled by anthocyanin solution. Results showed that under membrane thickness of 100 μm, coagulation temperature at room temperature, and evaporation time of 30 s, the optimum components in casting solution were 13% CA, 45% 1,4-dioxane, 31% acetone, 2% maleic acid, 3% PVP, and 6% methanol. In the concentration experiment, the prepared FO membrane showed water flux of 2.04 L m^?2 h^?1 and rejection rate of 98.61%. In the membrane cleaning experiment, the water flux of the FO membrane recovered 87.51% after rinsing for 1 h. The prepared membranes and previously published membranes were compared which showed the prepared membrane could significantly improve the rejection rate for anthocyanin solution.     

Synergetic cleaning procedure for a ceramic membrane fouled by beer microfiltration

Apart from considerations for hygienic operation, membrane cleaning is essential to maintain consistent permeability and selectivity of membrane systems for clarifying beer and beverages where balanced fractionation of particles/macromolecules is necessary. Experiments involved formulating and optimising chemical cleaning methods for a ceramic microfiltration membrane, which had been severely fouled during clarification of a commercial beer. The cleaning processes employed NaOH, HNO₃, H₂O₂, and Ultrasil 11 as the chemical cleaning agents. The cleaning ability and cleaning kinetics of the processes were evaluated in parallel with the study of the fouling mechanism, formation and strength so as to elucidate the synergetic relationship between fouling and cleaning. A three-step cleaning mechanism was postulated. This led to the development of a fast and effective combined simultaneous caustic cleaning and oxidation method (CSCCO), which was able to restore 87% of the original membrane's water permeability within 8 min. Analysis suggested the concept of a cleaning energy barrier E_c and a cleaning rate constant k_c0. This study confirmed the existence of a synergetic relationship between the prior fouling and optimum formulation of cleaner and optimal cleaning condition. The study varied beer filtration conditions. Transmembrane pressure (TMP) and crossflow velocity during fouling appeared to have a minimal effect on the membrane's subsequent cleanability, especially when the powerful CSCCO process was employed. The number of previous fouling/cleaning cycles was influential. A complete removal of the residual fouling, formed on the virgin membrane's surface proved beyond the means of the harsh chemical cleaning used under any conditions. The degree of residual fouling eventually reached a plateau and a level of 87% of the original water flux could be restored repeatedly.     

The effect of heat treatment of PES and PVDF ultrafiltration membranes on morphology and performance for milk filtration

The flat sheet polyethersulfone (PES) and poly(vinylidene fluoride) (PVDF) membranes were prepared by immersion precipitation technique. The influence of hot air and water treatment on morphology and performance of membranes were investigated. The membranes were characterized by AFM, SEM, cross-flow filtration of milk and fouling analysis. The PES membrane turns to a denser structure with thick skin layer by air treatment at various temperatures during different times. This diminishes the pure water flux (PWF). However the milk permeation flux (MPF) was considerably improved at 100 °C air treatment for 20 min with no change in protein rejection. The smooth surface and slight decrease in surface pore size for air treated PES membrane at 100 °C compared to untreated membrane may cause this behavior for the membrane. The water treatment of PES membranes at 55 and 75 °C declines the PWF and MPF and increases the protein rejection. This is due to slight decrease in membrane surface pore size. The treatment of PES membrane with water at higher temperature results in a porous structure with superior performance. The fouling analysis of 20 min treated membrane indicates that the surface properties of 100 °C air treated and 95 °C water treated PES membranes are improved compared to untreated membrane. The SEM observation depicts that the morphology of air and water treated PVDF membranes was denser and smoother with increasing the heat treatment temperature. The 20 min air treated PVDF membranes at 100 °C and water treated at 95 °C exhibited the highest performance and antifouling properties.     

Novel cellulose acetate membrane blended with phospholipid polymer for hemocompatible filtration system

To improve the blood compatibility of cellulose acetate (CA) membranes for hemofiltration, a novel CA membrane blended with 2-methacryloyloxyethyl phosphorylcholine (MPC) copolymer was designed for a hemocompatible filtration system. The MPC copolymer (PMB30) was synthesized from MPC and n-butyl methacrylate. The polymer solution for making the membrane was prepared from a solvent mixture composed of N,N-dimethylformamide, acetone, and 2-propanol. The CA and CA/PMB30 blended membranes with an asymmetric and porous structure were prepared by a phase inversion process. The mechanical properties and solute permeability of the CA/PMB30 blended membrane could be controlled by preparation conditions such as the composition of the solvents and the solvent evaporation time. The CA/PMB30 blended membrane showed both good water and solute permeabilities in comparison with the CA membrane. Also, the molecular weight of the solute passed through the membrane was changed by the addition of PMB30, and good permselectivity could be obtained. Moreover, the CA/PMB30 blended membranes had excellent blood compatibility such as protein adsorption resistivity compared to the CA membrane due to location of the MPC units in the PMB30 at the surface.     

成膜条件对聚醚砜超滤膜性能和结构的影响

以聚醚砜(PES)为膜材,聚乙二醇600(PEG600)为添加剂,N,N-二甲基甲酰胺(DMF)为溶剂,纯水为凝固浴,用相转化法制备聚醚砜超滤膜.详细探讨了PES浓度、添加剂含量、凝固浴温度对膜性能和结构的影响规律,确定了制备高水通量、高截留率聚醚砜超滤膜的最佳工艺条件.     

Improved microfiltration and bacteria removal performance of polyethersulfone membranes prepared by modified vapor‐induced phase separation

Polyethersulfone (PES) microfiltration membranes were fabricated by a combined vapor‐induced phase separation and wet phase separation method. The effect of different non‐solvent additives in casting solution, ie, acetone, diethylene glycol, and triethylene glycol (TEG) was investigated on the membrane morphology and performance. Scanning electron microscopy images showed that the membrane containing TEG additive had a skinless symmetric structure with well interconnected pores. The permeability of the PES/PVP/TEG membranes increased by decreasing PES and TEG and increasing PVP concentration. Bacteria removal performance of the prepared membranes was investigated by the filtration of E. coli suspension. The membrane made from casting solution containing 15 wt.% PES, 16 wt.% PVP, and 20wt.% TEG showed a pure water flux of ~ 5370 L/m² h at low transmembrane pressure of 10 psi and 100% bacteria removal efficiency. The results of in vitro cytotoxicity test and cell viability assay showed non‐toxic nature of the prepared membranes.     

Electrospun Polyacrylonitrile Nanofibrous Membranes for Point-of-Use Water and Air Cleaning

Novel electrospun polyacrylonitrile (PAN) nanofibrous membranes were prepared by using heat-press lamination under various conditions. The air permeability and the burst-pressure tests were run to select the membranes for point-of-use air and water cleaning. Membrane characterization was performed by using scanning electron microscopy, contact angle, and average pore size measurements. Selected membranes were used for both air dust filtration and cross-flow water filtration tests. Air dust filter results indicated that electrospun PAN nanofibrous membranes showed very high air-dust filtration efficiency of more than 99.99 % in between PM_0.3 and PM_2.5, whereas cross-flow filtration test showed very high water permeability over 600 L/(m²hbar) after 6 h of operation. Combining their excellent efficiency and water permeability, these membranes offer an ideal solution to filter both air and water pollutants.     

分子印迹膜萃取结合高效液相色谱-串联质谱法快速检测牛奶中的痕量环丙沙星残留

以聚偏氟乙烯膜为载体，恩诺沙星为伪模板分子，甲基丙烯酸为功能单体，乙二醇二甲基丙烯酸酯为交联剂，在氯仿-甲醇混合体系中制备恩诺沙星分子印迹膜（MIM），并将其作为分子印迹膜萃取（MIME）材料萃取牛奶样品中的环丙沙星，结合高效液相色谱-串联质谱（HPLC-MS/MS），快速检测牛奶中痕量环丙沙星残留。环丙沙星在0.1~200 μg/L范围内线性关系良好，相关系数为0.9996，检出限（S/N=3）和定量限（S/N=10）分别为0.02和0.10 μg/L。日间和日内精密度的相对标准偏差（RSD）在3.3%~7.9%之间。将开发的MIME-HPLC-MS/MS方法用于实际牛奶样品中环丙沙星加标回收率的检测，回收率在92.6%~119.1%之间。结果表明该方法前处理简单快速灵敏，检测准确度高，可用于牛奶样品中痕量环丙沙星残留的快速检测。     

Membrane fouling from ammonia recovery analyzed by ATR-FTIR imaging

The composition of the fouling layer formed during ammonia stripping via membrane distillation from model pig manure and the change in fouling composition as a result of three cleaning procedures was examined using ATR-FTIR imaging and k-means clustering. The use of ATR-FTIR imaging is advantageous as it is a label free technique that provides information on the chemical composition of the fouling as well as a high spatial resolution. The model manure was designed to resemble average Danish pig manure containing representative concentrations of inorganic and organic compounds and particle size distribution similar to the liquid fraction from mechanically separated manure. The fouling layer deposited on polypropylene, PP, and polytetrafluoroethylene, PTFE, membranes were investigated in combination with three cleaning procedures applying deionized water, 1 M NaOH solution followed by a 1 M citric acid solution or Novadan cleaning agents. The spectral data revealed that the fouling layer deposited on both PP and PTFE membranes before cleaning mainly consisted of carbohydrates, protein and lipids. Carboxylates and free fatty acids originating from reactions between NaOH and straw and proteins and lipids, respectively, and lignin were identified in some of the samples. The combination of PTFE membrane and Novadan cleaning agent resulted in the cleanest membranes, as only residual lipids were identified on these samples.     

Membrane formation mechanism and permeation properties of a novel porous polyimide membrane

The transport properties of a novel porous fluorinated polyimide membrane fabricated by a wet phase inversion process were studied with a stirred dead‐end filtration cell. The porous membrane‐forming solvents were tetrahydrofuran (THF), acetone, N,N‐dimethylacetamide (DMAc), N‐methylpyrrolidone (NMP), N,N‐dimethylformamide (DMF), and dimethylsulfoxide (DMSO). The phase separation phenomena in a ternary system of polyimide/solvent/water were investigated from cloud point curves by a titration method and binary interaction parameters. Solvent–water demixing in the system has been found to play very important roles in determining the structure and surface morphology of the polyimide membrane. The porous fluorinated polyimide membranes showed pore sizes from 4 to 500 nm and permeation properties from ultrafiltration to a microfiltration range. In this study, we particularly focused on fouling of the polyimide membranes, because fouling decreases the flux and increases the resistance. Interestingly, the porous polyimide membrane showed excellent water flux recovery after water cleaning compared with that of the polyethersulfone (PSf) membrane, which suggest that for a 6FDA‐6FAP membrane, the protein–membrane and protein–protein interaction was not so strong compared with those in a PSf membrane. Copyright © 2002 John Wiley & Sons, Ltd.     

乳状液膜法分离水中的铬

乳状液膜法由于其独特的物理化学性质,已广泛用于金属离子的萃取分离[1～3]。本文以span80-煤油-NaOH液膜体系分离水中铬。不加流动载体,利用内、外相中被分离物的浓度梯度实现物质迁移。当Cr2O2-7进入内相时,与内相的NaOH发生反应,在内相高浓度的NaOH存在下,可保持Cr2O2-7在液膜两侧有最大的浓度梯度,促使Cr2O2-7的迁移,实现Cr2O2-7与外相溶液的分离。1　实验部分1 1　仪器与试剂D40-1型电动搅拌器(杭州仪表电机厂),78-1型磁力加热搅拌器(江苏金坛新一佳仪器厂),721型分光光度计(上海第三分析仪器厂)。铬标准溶液(100ml/L):准…     

Fabrication,characterization and photoelectrochemical performance of chromium-sensitized titania nanotubes as efficient photoanodes for solar water splitting

Chromium-sensitized titanium dioxide nanotubes (CTNT) with high photocatalytic activity were prepared by a chemical bath deposition technique. The resulting films were characterized by SEM, EDX, and XRD. Results showed that the fabricated films have the ordered nanotubes with diameter of 90–140 nm, wall thickness of 20–50 nm, and tube lengths in the range of 24 μm. Diffuse reflectance spectra showed an increase in the visible absorption relative to bare titanium dioxide nanotubes (TNT). The photoelectrochemical performance was examined under light irradiation in 1 M NaOH electrolyte. Photoelectrochemical characterization shows that chromium sensitizing efficiently enhances the photocatalytic water splitting performance of CTNT composite. The sample (C3TNT) exhibited better photocatalytic activity than the TNT and CTNT fabricated using other chromium concentrations. This inexpensive photoanodes prepared free of noble metals showed enhanced high photocurrent density with good stability and is a highly promising photoanode for solar hydrogen production.     

Effect of liquid-liquid demixing on the membrane morphology,gas permeation,thermal and mechanical properties of cellulose acetate hollow fibers

The polymer/solvent/nonsolvent systems with different L-L demixing rates were prepared by employing a binary solvent mixture consisting of two solvents - one exhibits an instantaneous liquid-liquid (L-L) demixing process, while the other exhibits a delayed L-L demixing process. It was found that an increase in the delay time of L-L demixing results in a denser membrane structure, an increase in fiber mechanical strength, a delay desorption of moisture in membrane, and a decrease in gas permeance, for a hollow fiber fabrication system consisting of cellulose acetate (CA) (polymer), N-methyl-pyrrolidone (NMP) (solvent having an instantaneous L-L demixing property), tetrahydrofuran (THF) (solvent having a delayed L-L demixing property) and water (nonsolvent). Hollow fibers prepared under an instantaneous L-L demixing process tends to have more mechanically weak points (flaws) than those prepared under a delayed L-L demixing process. Surprisingly, SEM observation suggests that membranes wet-spun from solutions containing both THF and NMP tend to have a rough outer skin morphology. Inconsistent demixing and the collapse of the outer nascent skin may be the main causes. In addition, the effect of bore fluid chemistry on fiber performance is much more pronounced for systems having a delayed L-L demixing mechanism than that having an instantaneous L-L demixing.     

Photografted thin polymer hydrogel layers on PES ultrafiltration membranes: characterization, stability, and influence on separation performance

Highly fouling-resistant ultrafiltration (UF) membranes were synthesized by heterogeneous photograft copolymerization of two water-soluble monomers, poly(ethylene glycol) methacrylate (PEGMA) and N,N-dimethyl-N-(2-methacryloyloxyethyl-N-(3-sulfopropyl)ammonium betaine (SPE), with and without cross-linker monomer N,N'-methylene bisacrylamide (MBAA), onto a polyethersulfone (PES) UF membrane. The characteristics, the stability, and the UF separation performance of the resulting composite membranes were evaluated in detail. The membranes were characterized with respect to membrane chemistry (by ATR-IR spectroscopy and elemental analysis), surface wettability (by contact angle), surface charge (by zeta potential), surface morphology (by scanning electron microscopy), and pure water permeability and rejection of macromolecular test substances (including the "cutoff" value). The surface chemistry and wettability of the composite membranes did not change after incubating in sodium hypochlorite solution (typically used for cleaning UF membranes) for a period of 8 days. Changes in water permeability after static contact with solutions of a model protein (myoglobin) were used as a measure of fouling resistance, and the results suggest that PEGMA- and SPE-based composite membranes at a sufficient degree of graft modification showed much higher adsorptive fouling resistance than unmodified PES membranes of similar or larger nominal cutoff. This was confirmed in UF experiments with myoglobin solutions. Similar results, namely, a very much improved fouling resistance due to the grafted thin polymer hydrogel layer, were also obtained in the UF evaluation using humic acid as another strong foulant. In some cases, the addition of the cross-linker during modification could improve both permeate flux and solute rejection during UF. Overall, composite membranes prepared with an "old generation" nonfouling material, PEGMA, showed better performance than composite membranes prepared with a "new generation" one, the zwitterionic SPE.     

UF of pulp and paper effluent: membrane fouling-prevention and cleaning

Effluent arriving from the Mondi Kraft paper mill at Piet Retief, South Africa, was filtered through tubular poly(ether sulphone) (PES) ultrafiltration membranes under constant pressure cross-flow conditions. The effluent that was fed into the membranes and permeate produced during filtration were characterised by UV–VIS light-spectroscopy. Substances that absorbed onto membranes during filtration caused changes to the permeability characteristics of the membranes. Changes in membrane performance were monitored by pure-water and product flux (pf) measurements.A colourimetric staining technique was developed to determine the nature of foulants adsorbed onto the membranes. Membrane cleaning solutions were subsequently selected using information obtained from the characterisation studies. In addition, the anti-fouling potential of non-covalently attached coating materials was investigated as a possible membrane pretreatment technique. Results showed that foulants present in the effluent are of phenolic and hydrophobic nature. Increasing the hydrophilic characteristics of membranes prior to filtration could reduce the amount of organic foulants that adsorbed onto the membranes. Membrane pretreatment not only reduced fouling, but also improved the effectiveness of cleaning methods. Membranes were effectively cleaned by a combination of mechanical and chemical cleaning techniques.     

用于碱性膜燃料电池的新型聚苯醚阴离子交换膜的制备与性能

以2,6-二甲基聚苯醚(PPO)为原料, 经溴代及N-甲基咪唑季铵化反应, 制备了N-甲基咪唑季铵化PPO, 并进行了红外光谱(FTIR)和氢核磁共振波谱(¹H NMR)表征.所得季铵化产物与聚乙烯醇(PVA)按不同比例共混后用戊二醛交联成膜, 在碱性液中浸泡转化为OH^-型, 得到一系列阴离子交换膜.通过扫描电子显微镜(SEM) 、交流阻抗(AC)、拉伸实验和热重分析(TGA)等手段考察了膜的微观形貌及电导率、力学性能、热稳定性及耐碱性等性能.结果表明, 膜的外观形貌平整均一; 含水率为50.4%~151.2%; 溶胀度为79.2%~164.2%; 离子交换容量为0.47~1.52 mmol/g; 90℃时, M4膜的电导率高达49.1 mS/cm; 断裂伸长率达到128%, 极大改善了PPO膜应力易裂的状况.同时, N-甲基咪唑鎓基团分解温度达到170℃, 高于常用的阴离子交换膜中的季铵基团(120℃).在2 mol/L的NaOH溶液中浸泡192 h后, 电导率仅下降19%, 具备良好的耐碱性能力.     

Surface modification of polysulfone ultrafiltration membranes and fouling by BSA solutions

Five different chemically modified versions of polysulfone were prepared via two different homogeneous chemical reaction pathways. They, together with the base polymer, were cast as membranes by a phase-inversion process. The surface energies of these membranes, as measured by contact angles, were used to characterize the different membranes. Streaming-potential measurements were obtained to probe the surface charge of the membranes. The surface roughness of each membrane was also determined by atomic-force microscopy. Each membrane was then exposed to deionized water, 0.08 g/l bovine serum albumin solution and deionized water using a standard filtration procedure to simulate protein fouling and cleaning potential.Both the chemistry and the size of the grafted molecules were correlated with respect to volumetric flux during ultrafiltration of protein solutions. Surface roughness seemed to be important for filtering pure water. Hysteresis between advancing and receding contact angles increased with hydrophilicity of the membrane surfaces. One possible explanation could be that surface reorientation was more likely with hydrophilic than with hydrophobic membranes. The membrane modified by direct sulfonation had the lowest surface energy and the shortest grafted chain length and exhibited the highest volumetric flux with BSA solution. It was also the easiest to clean and exhibited the highest initial flux recovery by stirring (91%) and backflush (99%) methods with deionized water. In most cases, backflushing rather than stirring was more effective in recovering the water flux.