Preparation and characterization of poly (methyl methacrylate) and sulfonated poly (ether ether ketone) blend ultrafiltration membranes for protein separation applications

Poly (methyl methacrylate) (PMMA) and poly (methyl methacrylate)/sulfonated poly (ether ether ketone) (SPEEK) blend membranes were prepared by phase inversion technique in various composition using N,N'-dimethylformamide as solvent. The prepared membranes were characterized in terms of pure water flux, water content, porosity and thermal stability. The addition of SPEEK to the casting solution resulted in membranes with high pure water flux, water content, porosity and slightly low thermal stability. The cross sectional views of the blend membranes under electron microscope confirm the porosity and water flux results. The effect of the addition of SPEEK into the PMMA matrix on the extent of bovine serum albumin (BSA) separation was studied. It was found that the permeate flux increased significantly while the rejection of BSA from aqueous solution reduced moderately during ultrafiltration (UF) process. The effect was attributed to the increase in porosity and charge of the membrane due to the addition of SPEEK into the PMMA blend solution.     

Toxic metal ion separation by cellulose acetate/sulfonated poly(ether imide) blend membranes: effect of polymer composition and additive

Toxic heavy metal ion removal from industrial effluents are gaining increased visibility owing to environmental concern and saving precious materials. In this work, an attempt has been made to remove the valuable metal ions using modified ultrafiltration (UF) blend membranes based on cellulose acetate (CA) and sulfonated poly(ether imide) (SPEI) were prepared in the presence and absence of additive, poly(ethylene glycol) 600 (PEG600) in various compositions. Prepared membranes were characterized in terms of pure water flux (PWF), water content and membrane hydraulic resistance. High flux UF membranes were obtained in the range of 15-25 wt% SPEI and 2.5-10 wt% PEG600 in the polymer blend. The molecular weight cut-off (MWCO) of the blend membranes were determined using protein separation studies found to vary from 20 to greater than 69 kDa. Surface morphology of the blend membranes were analysed with scanning electron microscopy. Studies were carried out to find the rejection and permeate flux of metal ions such as Cu(II), Ni(II), Zn(II) and Cd(II) using polyethyleneimine as the chelating ligand. On increasing the composition of SPEI and PEG600, the rejection of metal ions is decreasing while the permeate flux has an increasing trend. These effects are due to the increased pore formation in the CA/SPEI blend membranes because of the hydrophilic SPEI and polymeric additive PEG600. In general, it was found that CA/SPEI blend membranes displayed higher permeate flux and lower rejection compared to pure CA membranes. The extent of separation of metal ions depends on the affinity of metal ions to polyethyleneimine to form macromolecular complexes and the stability of the formed complexes.     

TiO2纳滤膜对重金属离子的截留性能

采用孔径为1.5 nm的TiO2纳滤膜,在压力0.4～0.8 MPa,pH值3～7的条件下,考察了膜对浓度范围为50～500 mg/L的Cu(NO3)2、Ni(NO3)2、ZnC12和CdC12四种单组份重金属溶液的截留性能.结果表明:除Cd2+外,膜对重金属离子的截留率随溶液浓度的增大先增大,当浓度达到200 mg/L后趋于稳定;升高压力膜的离子截留率会略有增加;当pH=6时,膜对Ni2+和Cd2+的截留率最低,而对Cu2+和Zn2+的截留率在pH=5～6时达到最高.TiO2膜对Cu2+、Ni2+、Zn2+和Cd2+的最高截留率分别可以达到96.9％、95.9％、92.5％和83.2％.     

Optimization using central composite design (CCD) for the biosorption of Cr(VI) ions by cross linked chitosan carbonized rice husk (CCACR)

The presence of heavy metals in aqueous streams arising from the discharge of industrial effluents into water bodies is one of the most important environmental issues because of their toxic nature and its removal is highly essential. This paper deals with the adsorption studies for the removal of hexavalent chromium ions from aqueous solutions using Schiff based chitosan activated carbonized rice husk composites as adsorbent. The activation and surface properties of the adsorbent were characterized by Scanning Electron Microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), and Brauner Emmet and Teller (BET) analyzer. Central Composite Design (CCD) was used to optimize the process variables such as initial metal ion concentration, adsorbent dosage and pH of the solution on the performance of percentage removal and adsorption capacity. The experimental data were validated with different isotherms and kinetic models to evaluate the solute interaction behavior and nature of adsorption.     

Cellulose Acetate and Polyetherimide Blend Ultrafiltration Membranes, I: Preparation, Characterization, and Application

Ultrafiltration (UF) techniques have particular advantages for simultaneous purification, concentration, and fractionation of macromolecules. In this study, polymeric blend ultrafiltration membranes based on cellulose acetate and polyetherimide were prepared by phase inversion technique and characterized in terms of compaction time, pure water flux (PWF), water content, membrane hydraulic resistance, and scanning electron microscopy (SEM). The blend membranes prepared were subjected to the separation of macromolecular proteins such as bovine serum albumin (BSA), egg albumin (EA), pepsin, and trypsin. The molecular weight cut-off (MWCO) of blend membranes obtained from the protein separation studies is also presented. Toxic heavy metal ions such as copper, nickel, zinc, and cadmium were subjected to separation by the blend membranes by complexing them with the polymeric ligand polyethyleneimine. The separation and permeate flux efficiencies of the blend membranes are compared with those of pure cellulose acetate membranes.     

有机相纳滤分离过程中浓度、电荷、溶剂对溶质截留行为的影响

研究了浓度、电荷和溶剂对膜通量和溶质截留率的影响．结果表明,在有机相中,溶质的截留率随浓度的增加而增加,该结果与水相纳滤的规律相反,通量衰减系数的分析结果发现,浓差极化是导致该结果的原因之一．溶质所带电荷对水相中的溶质截留率影响显著,但对有机相中的截留率影响很小,有机相中纳滤膜分离的主要机理为筛分效应。溶剂的粘度和极性是影响膜通量的主要因素,对于疏水性纳滤膜MPF-50,通量随黏度的增加而降低,溶剂极性与通量关系不明显;对于亲水性纳滤膜MPF-44,通量随极性的降低而降低,而与黏度关系不明显．在纯有机溶剂中,大豆异黄酮D的截留率随溶剂极性的增加而升高．但在甲醇-水的混合溶液中,大豆异黄酮D的截留随溶剂极性的增加而降低．目前普遍认为对于同种纳滤膜,相同有机分子在有机相中的截留率低于水中的截留率,但本文的研究发现,对MPF-50膜,大豆异黄酮D在甲醇和丙酮中的截留率反而显著高于水中的截留率,对该现象的解释有待进一步研究．     

聚砜/聚醚类高聚物共混相容性及超滤膜的研究

研究了由聚砜(PSf)和自制的聚醚类高聚物制备的共混超滤膜的组分相容性、性能及膜结构．利用差示扫描量热仪(DSC)测定了纯PSf、纯聚醚类高聚物以及不同PSf／聚醚类高聚物共混配比制得的超滤膜的玻璃化转变温度(Tg)．实验结果表明,PSf与聚醚类高聚物组分在整个配比范围内完全相容．所测定的共混膜的Tg与利用Fox方程得出的理论计算值相一致．PSf／聚醚类高聚物共混膜的水通量要高于纯PSf和纯聚醚类高聚物且截留率几乎没有变化．通过扫描电子显微镜(SEM)观察了膜的形态并对膜的超滤性能进行了解释．     

Removal of chromium ions from aqueous solutions by polymer-enhanced ultrafiltration

This study deals with the removal of chromium species from aqueous dilute solutions using polymer-enhanced ultrafiltration (PEUF) process. Three water soluble polymers, namely chitosan, polyethyleneimine (PEI) and pectin were selected for this study. The ultrafiltration studies were carried out using a laboratory scale ultrafiltration system equipped with 500,000 MWCO polysulfone hollow fiber membrane. The effects of pH and polymer composition on rejection coefficient and permeate flux at constant pressure have been investigated. For Cr(III), high rejections approaching 100% were obtained at pH higher than 7 for the three tested polymers. With chitosan and pectin, Cr(VI) retention showed a slight increase with solution pH and did not exceed a value of 50%. An interesting result was obtained with PEI. The retention of Cr(VI) approached 100% at low pH and decreased when the pH was increased. This behavior is opposite to what one can expect in the polymer-enhanced ultrafiltration of heavy metals. Furthermore, the concentration of polymer was found to have little effect on rejection. Permeate flux remained almost constant around 25% of pure water flux.     

聚乙二醇丙烯酸酯表面改性聚醚砜酮微孔膜的结构和性能

为了提高聚醚砜酮(PPESK)微孔膜的亲水性和抗污性,采用紫外(UV)辐照引发聚乙二醇丙烯酸酯(PEGA)在膜上发生接枝和交联,在膜表面形成稳定的亲水层.利用场发射扫描电镜(SEM)研究了固定PEGA后PPESK膜表面形貌的变化.表面改性后PPESK膜的水接触角的降低表明PEGA的固定有利于提高其亲水性,蛋白质静态吸附实验显示膜的抗蛋白质污染能力增强,渗透实验表明膜表面较低数量的PEGA亲水链有利于提高PPESK微孔膜的水通量,膜的溶质截留率增大,截留分子量(MWCO)减小.     

Investigation of process performance and fouling mechanisms in micellar-enhanced ultrafiltration of nickel-contaminated waters

Nickel removal from aqueous solution by micellar-enhanced ultrafiltration (MEUF) with relatively low transmembrane pressures was investigated at varying conditions of sodium lauryl ether sulfate (SLES) and nickel concentrations, transmembrane pressure and sodium chloride content. Process employed in continuous filtration mode, could be operated within a short time of 30 min presenting high rejection of nickel and SLES at high transient fluxes. Under the effect of increasing transmembrane pressure, the rejection of nickel and SLES increased, but the transient flux decreased. The existence of salt caused to decrease both rejections and flux. Nickel rejection, SLES rejection and flux were established as 98.6%, 75.7% and 0.304 m(3)/m(2)h, respectively, for the conditions of surfactant to metal (S/M) ratio of 10 (SLES = 2 mM), transmembrane pressure of 250 kPa without NaCl content at the end of 90-min operation time. The analyses related to the membrane fouling were carried out using adsorptive fouling models. It has been determined that, the fouling occurs as a dynamic function of various process conditions studied, and depends strongly on mechanisms controlled by the formation of gel layer and its bridging over the pore entrances simultaneously together with partial constriction of membrane pores by surfactant adsorption.     

应用纳滤膜分离糖和盐的实验研究

选择NF-45纳滤膜进行糖和盐单组分和混合体系的分离实验研究,考察了纳滤膜分离性能随着操作压力、循环流量及料液浓度的变化所受到的影响。讨论了葡萄糖-氯化钠、蔗糖-氯化纳混合体系中糖和盐的相互影响作用,认为可以运用NF-45纳滤膜在适宜的操作条件（如操作压力、料液浓度）实现糖和盐的较好分离。     

Phase behaviour and mechanical properties of poly(ether ether ketone)-poly(ether sulphone) blends

The phase behaviour and the mechanical properties of binary blends composed of poly(ether ether ketone) and poly(ether sulphone) have been studied both in the amorphous state and after crystallization of poly(ether ether ketone).Differential scanning calorimetry and dynamical mechanical analysis clearly show the existence of phase separation in the blends. Density measurements confirm the absence of strong interactions between the blend components, as well as the slight effect of PES on the crystallization of PEEK.The mechanical properties of the quenched, amorphous blends remain surprisingly good in spite of the observed immiscibility, however, slowly cooled, crystalline blends appear as brittle materials.     

热致相分离法制备平片式EVOH微孔膜研究

采用热致相分离方法,选择乙烯的摩尔分数为32%的乙烯-乙烯醇共聚物(EVOH)为原料,丙三醇为稀释剂制备了亲水性高分子平片式微孔膜,并研究了体系组成、冷却速率等对膜的结构和性能的影响.测试了膜的纯水通量、截留率和孔隙率,用泡点法测得了平均孔径.并用扫描电子显微镜(SEM)表征了微孔膜的断面形态.结果表明:分相的方式及微孔的形态由体系组成及冷却速率决定.降低聚合物浓度,延缓冷却速率,都有利于较大孔径膜的生成并得到较大的纯水通量和孔隙率,同时截留性能有所下降.     

Application of nanofiltration for chromium concentration in the tannery wastewater

The article presents results of investigation concerning an influence of tannery wastewater composition on chromium(III) concentration in the wastewaters during the nanofiltration process (NF). The effectiveness of this process strongly depends on mutual relation between chloride and sulfate ions concentration in tannery wastewater. For this reason, the optimum composition of the tannery wastewater should consist chloride/sulfate ions ratio close to 1. Moreover, an influence of transmembrane pressure (TMP) and the "ageing" of chromium tannery wastewater on the efficiency of the process has been investigated. Optimal range of TMP equal to 14-16 bar has been assumed for the process. It is necessary to point out that the optimum transmembrane pressure can be changed in the case of the membranes with different permeation properties. "Ageing" of the tannery wastewater reduces only a little an efficiency of the process. Experimental results demonstrated that the NF process could be successfully used for the concentration of chromium in the tannery wastewater with high permeate flux, selectivity and performance stability.     

乙醚对酚酞基聚芳醚砜超滤膜性能和结构的影响

以新型耐高温工程塑料——含酚酞侧基的聚芳醚砜(PES-C)为膜材料,N,N-二甲基乙酰胺(DMAc)为溶剂,加入一种易挥发添加剂:乙醚.通过改变铸膜液中添加剂乙醚的含量,采用相转化法在平板刮膜机上制备了一系列超滤膜,考察了添加剂乙醚含量对铸膜液黏度、凝胶速度、膜性能和结构的影响,研究了PES-C/DMAc体系中添加剂乙醚作用的规律.结果发现,乙醚的加入,会使溶剂对聚合物溶解能力降低.乙醚含量的增加,使铸膜液黏度增加,凝胶速度下降,水通量降低,截留率上升.所制备的超滤膜的结构为指状孔结构,但是随着乙醚用量的增加,皮层增厚,过渡层中指状孔减少.     

Sorption, diffusion, and pervaporation characteristics of dimethylformamide/water mixtures using sodium alginate/polyvinyl pyrrolidone blend membranes

Separation of aqueous dimethylformamide (DMF) solutions in the concentration range of 0-100 wt% were studied using sodium alginate (NaAlg)/polyvinyl pyrrolidone (PVP) blend membranes. The NaAlg was blended in different ratios with PVP. Prepared membranes were crosslinked with CaCl₂ for testing in pervaporation (PV) separation of DMF/water mixtures. Effects of feed composition (0-100 wt%), operating temperature (30-50 °C), and membrane thickness were investigated. Best results were obtained at the conditions of 75/25 NaAlg/PVP blend ratio (w/w), 40 °C temperature, 20 wt% DMF concentration, and 70 μm membrane thickness. Blending of PVP with NaAlg increased permeation flux whereas it decreased the separation factor. NaAlg/PVP membranes gave separation factors of 5.5-27 for permeation flux of 0.96-1.81 kg/m²h depending on the operating temperature and the feed mixture composition. Arrhenius plot of permeation flux data versus reciprocal of temperature exhibited linear trends. Permeation activation energy of DMF and water in the PV was calculated as 6.76 and 1.88 kcal/mol, respectively, using an Arrhenius type relationship. Sorption-diffusion properties of the NaAlg/PVP membranes were also investigated at the operating temperature and the feed composition.     

Removal of toxic chromium from wastewater using green alga Ulva lactuca and its activated carbon

Biosorption of heavy metals can be an effective process for the removal of toxic chromium ions from wastewater. In this study, the batch removal of toxic hexavalent chromium ions from aqueous solution, saline water and wastewater using marine dried green alga Ulva lactuca was investigated. Activated carbon prepared from U. lactuca by acid decomposition was also used for the removal of chromium from aqueous solution, saline water and wastewater. The chromium uptake was dependent on the initial pH and the initial chromium concentration, with pH approximately 1.0, being the optimum pH value. Langmuir, Freundlich, Redlich-Peterson and Koble-Corrigan isotherm models were fitted well the equilibrium data for both sorbents. The maximum efficiencies of chromium removal were 92 and 98% for U. lactuca and its activated carbon, respectively. The maximum adsorption capacity was found to be 10.61 and 112.36 mg g(-1) for dried green alga and activated carbon developed from it, respectively. The adsorption capacities of U. lactuca and its activated carbon were independent on the type of solution containing toxic chromium and the efficiency of removal was not affected by the replacing of aqueous solution by saline water or wastewater containing the same chromium concentration. Two hours were necessary to reach the sorption equilibrium. The chromium uptake by U. lactuca and its activated carbon form were best described by pseudo second-order rate model. This study verifies the possibility of using inactivated marine green alga U. lactuca and its activated carbon as valuable material for the removal of chromium from aqueous solutions, saline water or wastewater.     

γ-Alumina composite membranes modified with microporous silica for CO2 separation

-Al2O3 composite membranes have been modified with microporous silica layers to improve the separation factor of CO2 to N2. From the analysis of micropore volume fraction and CO2 adsorption behaviour of SiO2 unsupported membranes, it was found that the SiO2 membrane layer feasible to separate CO2 could be obtained from a sol prepared by hydrolysis of tetraethyl orthosilicate in aqueous nitric acid solution (acid concentration of 0.001 M and sol pH of 2.0). The unsupported membrane prepared from this optimum sol had a micropore volume fraction of 0.85 and CO2 adsorption amount of 27 cm3(STP)g–1 at 0.1 MPa and 25°C. Defect-free silica modified -Al2O3 membranes could besynthesized by dipcoating or pressurized coating from outside the support. The CO2/N2 separation factor of these membranes varied severely with the separation process parameters, such as transmembrane pressure, stage cut and CO2 concentration in feed gas. -Al2O3 membranes modified by dipcoating and pressurized coating had a CO2/N2 separation factor of 2.4 and 1.45, respectively, at P = 0.3 MPa, stage cut = 0.1, and 25°C for a CO2 feed gas mole fraction of 0.5. The CO2/N2 separation factor at 25°C decreased with increasing heat-treatment temperature. The main mechanisms of CO2 permeation through silica modified membranes were surface diffusion and Knudsen diffusion.     

Osmotic-pressure model with permeability analysis for ultrafiltration in hollow-fiber membrane modules

The effects of operating conditions on the permeate flux for ultrafiltration of aqueous solutions of Dextran and Polyvinylpyrrolidone in hollow-fiber membrane modules have been investigated experimentally based on the osmotic-pressure model with the permeability analysis. The correlation equations for pure-water permeability after solute adsorption and fouling on the membrane have been obtained as functions of the transmembrane pressure and solution concentration. The theoretic prediction of permeate fluxes agrees well in tendency with the experimental data.     

Effect of blending ratio on pervaporative separation of 1,4-dioxane/water mixtures through PVA-PEI membranes

Blend membranes were made by mixing aqueous solutions of hydrophilic polymers poly(vinyl alcohol) (PVA) and polyethyleneimine (PEI) in different ratios for investigating the separation of 1,4-dioxane/water azeotropic mixture by pervaporation (PV). Water forms azeotrope at 18 wt% concentration with 1,4-dioxane. The resulting membranes were characterized by FTIR to verify the interaction between the homopolymers, wide-angle X-ray diffraction (WAXD) to observe the effect of blending on crystallinity and thermal gravimetric analysis (TGA) to investigate the thermal stability. Sorption studies were carried out to evaluate the extent of interaction and degree of swelling of the blend membranes in pure liquids as well as binary mixtures. The effect of blend composition ratio on membrane parameters such as flux and selectivity was analyzed. An increase in PVA content in the blend caused a reduction in the flux and an increase in selectivity. Among the blends tested in the study, the 5:1 PVA/PEI blend membrane showed the highest separation factor of 44.01 and exhibited a flux of 0.733 kg/m² h 10 μm for azeotropic feed composition at ambient temperature (30 °C).