Non-invasive monitoring of fouling in hollow fiber membrane via UTDR

Fouling is the most critical problem associated with membrane separations in liquid media. But it is difficult to control the inevitable membrane fouling because of its invisibility, especially on the inside surface of hollow fiber membranes. This study describes the extension of ultrasonic time-domain reflectometry (UTDR) for the real-time measurement of particle deposition in a single hollow fiber membrane. A transducer with a frequency of 10 MHz and polyethersulfone hollow fiber membranes with 0.8 mm inside diameter (ID) and 1.2 mm outside diameter (OD) were used in this study. The fouling experiments were carried out with 1.8 g/L kaolin suspension at flow rates 16.7 and 10.0 cm/s. The results show that UTDR technique is able to distinguish and recognize the acoustic response signals generated from the interfaces water/upper outside surface of the hollow fiber, lumen upside surface/water, water/lumen underside surface and lower outside surface/water in the single hollow fiber membrane module in pure water phase. The systemic changes of acoustic responses from the inside surfaces of the hollow fiber in the time- and amplitude-domain with operation time during the fouling experiments were detected by UTDR. It is associated with the deposition and formation of the kaolin layer on the inside surfaces. Further, the acoustic measurement indicates that the deposited fouling layer is denser on the lumen underside surface of the hollow fiber than that on the lumen upside surface as a result of weight. Moreover, it is found that the fouling layer grows faster on the inside surface of the hollow fiber at a flow rate of 10.0 cm/s than that at 16.7 cm/s due to the lower shear stress. The fouling layer formed is thicker at a flow rate of 10.0 cm/s than that at 16.7 cm/s. The flux decline data and SEM analysis corroborate the ultrasonic measurement. Overall, this study confirms that UTDR measurement will provide not only a new protocol for the observation of hollow fiber membrane fouling and cleaning, but also a quantitative approach to the optimization of the membrane bioreactor system.     

Innovative beneficial reuse of reverse osmosis concentrate using bipolar membrane electrodialysis and electrochlorination processes

Reverse osmosis (RO) is a widely used and rapidly growing desalination technology. A major disadvantage of this process is that the concentrate from the RO process, which could be as much as 25% of the feed stream, represents a polluting stream. This waste stream could pose a significant challenge to the implementation of this process, particularly for inland communities which do not have the option of ocean disposal. An excellent environmentally benign approach to disposal could be beneficial reuse of the waste stream. This study presents two innovative beneficial reuse strategies for RO concentrate produced by an integrated membrane system (IMS) from a wastewater reclamation facility. The technologies evaluated in this study included bipolar membrane electrodialysis (BMED) for conversion of RO concentrate into mixed acid and mixed base streams, and electrochlorination (EC) for onsite chlorine generation. Bench-scale studies conducted with BMED demonstrated that RO concentrate could be desalted while producing mixed acids and mixed bases with concentrations as high as 0.2N. Similarly, the EC process was capable of producing a 0.6% hypochlorite solution from RO concentrate. The acids and bases as well as the hypochlorite produced could be directly applied to the RO process as well as upstream pre-treatment processes. A preliminary economic evaluation of the viability of these two approaches was conducted by conducting rough order of magnitude cost estimates based on the bench-scale performance of these processes on RO concentrate. A comparison of the overall costs of an Integrated Membrane System utilizing these innovative reuse strategies with conventional disposal options and thermal zero liquid discharge treatment is presented. This comparison indicates that a reuse approach might be economically viable for inland wastewater reuse facilities that utilize RO membranes and have limited options for concentrate disposal.     

Synthesis and property of a novel sulfonated poly(ether ether ketone) with high selectivity for direct methanol fuel cell applications

A novel membrane material based on random copolymer composed of poly(acrylonitrile-([3-(methacryloylamino)propyl]-dimethyl(3-sulfopropyl) ammonium hydroxide)) (PAN–MPDSAH) was synthesized by the water phase suspension polymerization. The zwitterionic PAN-based membranes were prepared through blending PAN and PAN–MPDSAH copolymer by a phase inversion method. The zwitterionic PAN-based membranes have higher hydrophilicity and wettability, and lower protein adsorption in comparison with the control PAN membrane. Ultrafiltration experiments revealed that membrane fouling, especially irreversible membrane fouling, for the zwitterionic PAN-based membranes is remarkably reduced due to the incorporation of zwitterionic PMPDSAH segments on the membrane surfaces. Moreover, the reversible membrane fouling during ultrafiltration process can be easily washed away by simple water cleaning. The zwitterionic PAN-based membranes can run for a long time and be reused without significant decrease of separation performance.     

The interaction of water vapors with H3PO4 imbibed electrolyte based on PBI/polysulfone copolymer blends

The interaction of steam with phosphoric acid imbibed electrolyte composed of PBI/PPy(50)coPSF 50/50 polymer blend and its effect on fuel cell performance was studied regarding its permeability through and its chemical interaction with the membrane. It was found that steam is the only gas that permeates the membrane with a permeability coefficient 1.1 × 10⁻¹⁴ mol cm cm⁻² s⁻¹ Pa⁻¹ at 150 °C. This is attributed either to the high solubility of water in phosphoric acid or to the chemical interaction with pyrophosphoric acid_. The latter was demonstrated by carrying out TGA experiments under various water vapor partial pressures. Water reacts with pyrophosphoric acid in order to maintain the equilibrium concentration of phosphoric acid at high level, thus improving proton conductivity and fuel cell performance. In addition it is shown that excess water dissolves in the membrane thus maintaining the “membrane/acid” system at high hydration level. This depends both on temperature and steam partial pressure. Although in the present study it is shown that steam plays a significant role in the performance of the high temperature Polymer electrolyte membrane (PEM) fuel cell, nevertheless its feed with humidified gases is not necessary, due to the back transport of the water produced at the cathode.     

High throughput screening and measurements of proton conductivity of newly developed PEM materials based on proton transport visualization

An electrochemical method for proton transport visualization was developed and applied to the investigation of proton-conducting membrane materials. The method employs the change in the visual appearance of chemo-chromic tungsten oxide WO₃ in the presence of atomic hydrogen. An all-solid electrochemical cell arranged by substituting a fuel cell cathode with a thin film of WO₃-electrode was built and shown to generate both optical and electrical response to hydrogen gas exposure. The design of the cell was extended to a high throughput screening system that was utilized to characterize proton transport properties of samples, including a number of new compounds synthesized in-house by sol–gel wet chemistry. Non-destructive introduction of superacidic groups promoting proton hopping in the membrane materials was achieved by photodecomposition of a photoacid generator just after membrane casting. A model quantitatively describing current–voltage relation in the cell was developed and successfully applied to derive area-specific resistance of proton-conductive membranes from the experimental results. Area-specific resistances of membranes are derived from the slopes of optically reconstructed voltage–current curves. Sensitivity and dynamic range of the screening method are discussed.     

Preparation and biodegradation of electrospun PLLA/keratin nonwoven fibrous membrane

As a kind of natural protein, wool keratin was used to improve the cell affinity of poly(l-lactic acid) (PLLA). After small keratin particles were prepared from keratin solution by spray-drying process, they were blended with PLLA solution. PLLA/keratin nonwoven fibrous membrane was produced by electrospinning the blend solutions. The release rate of keratin from the composite membrane was detected by Fourier transform infrared (FTIR) after PLLA/keratin membranes were degraded in PBS up to 4 weeks. The chemical compositions of the PLLA/keratin surface were examined by X-ray photoelectron spectroscope. Although more than half of the keratin was removed from PLLA/keratin membrane during the first few hours of degradation, some keratin particles were still embedded in the PLLA fibers. Osteoblast cells were used to evaluate the cellular behaviors of the composite membrane. After 7 days culturing, more cells were observed on PLLA/keratin membranes than on pure PLLA membranes. MTT assay and alkaline phosphatase (ALP) activity results suggested that keratin could improve the interactions between osteoblast cells and the polymeric membranes.     

多壁碳纳米管诱导A549细胞氧化应激与去极化线粒体膜电位

以人肺上皮细胞系A549为模型细胞, 探讨多壁碳纳米管的细胞毒性效应及其机制. A549细胞暴露于不同浓度(0~300 μg/mL)的多壁碳纳米管后, 用MTT比色法检测细胞活力和Hoechst 33342染色法观察细胞形态; 用活性氧(ROS)敏感探针2',7'-二氯荧光素二乙酸酯(DCFH-DA)结合流式细胞仪检测细胞内ROS水平; 用荧光探针JC-1结合激光共聚焦显微镜检测细胞线粒体膜电位ΔΨm的变化; 用免疫荧光和蛋白印迹法检测细胞氧化应激敏感蛋白血红素氧合酶-1(HO-1)的表达水平. 结果表明, 多壁碳纳米管可引起A549细胞活性降低、细胞内活性氧ROS过量产生以及谷胱甘肽GSH含量下降, 诱导细胞氧化应激效应; 抗氧化剂N-乙酰半胱氨酸(NAC)抑制多壁碳纳米管诱导的A549细胞内ROS的产生. 多壁碳纳米管处理A549细胞2 h后, 诱发细胞线粒体膜电位下降; 多壁碳纳米管诱导细胞氧化应激的同时伴有适应性应激蛋白HO-1的上调表达. 结果表明, 细胞氧化应激和线粒体膜电位去极化可能是多壁碳纳米管诱导A549细胞毒性效应的重要机制.     

Performance of a photocatalytic hybrid system coupled with a stainless steel membrane for removal of humic acid

The objective of this study was to evaluate the performance of a photocatalysis/H₂O₂/metal membrane hybrid system in the degradation of humic acid. A metal membrane of nominal pore size 0.5 μm was used in the experiment for separation of TiO₂ particles. Hydrogen peroxide was tested as an oxidant. The efficiency of removal of COD_Cr and color increased rapidly for initial hydrogen peroxide concentrations up to 50 mg L⁻¹. The efficiency of removal of COD_Cr and color by 50 mg L⁻¹ initial hydrogen peroxide concentration was approximately 95 and 98%, respectively. However, addition of hydrogen peroxide over 50 mg L⁻¹ inhibited the efficiency of the system. Addition of hydrogen peroxide to a UV/TiO₂ system enhanced efficiency of removal of COD_Cr and color compared with no addition of hydrogen peroxide. This may be ascribed to capture electrons ejected from TiO₂ and to the production of OH radicals. Application of the metal membrane in the UV/TiO₂/H₂O₂ system enhanced the efficiency of removal of COD_Cr and color because of adsorption by the metal membrane surface and the production of OH radicals. By application of a metal membrane with a nominal pore size of 0.5 μm, TiO₂ particles were effectively separated from the treated water by metal membrane rejection. The photocatalytic metal membrane had much less resistance than the humic acid, TiO₂, and humic acid/TiO₂ because of the degradation of humic acid by the photocatalytic reaction.     

Surface properties of new virginiamycin M1 derivatives

Three kinds of derivatives of the M₁ factor of virginiamycin have been synthesised: esters with long chain fatty acids, oximes with modified polar amino acids and bis-derivatives with both the ester and oxime function. The study of the surface tension time dependence of M₁ and its derivatives has shown that it is necessary to enhance simultaneously the hydrophobicity and the hydrophilicity of M₁ to render M₁ surface-active. A structure/function relationship study of the surface-active bis-derivatives has shown that enhancing the hydrophobicity of the molecule led to slower adsorption kinetics, higher stability of the monolayers formed and a better capacity to penetrate a membrane model. The repulsive electrostatic forces due to the presence of charges on the amino acids linked to M₁ lead to higher surface tensions, a greater molecular area at the interface and lower penetration into a membrane model.This study has demonstrated that modifying systematically the hydrophobicity and hydrophilicity of a non surface-active molecule allows the production of surface-active derivatives.     

SPEEK/PES-C、SPEEK/SPES-C共混质子交换膜研究

通过在磺化聚醚醚酮(SPEEK,DS=61.68%)中分别混入酚酞型聚醚砜(PES-C)、磺化酚酞型聚醚砜(SPES-C,DS=53.7%)制备出SPEEK/PES-C、SPEEK/SPES-C共混质子交换膜.结果表明,共混的两种聚合物之间均具有较好的相容性.PES-C、SPES-C的混入能有效降低膜的溶胀及甲醇透过,且随着共混量的增加,这种作用越趋明显.纯SPEEK膜在75℃左右溶解,而SPEEK/PES-C(30wt%)、SPEEK/SPES-C(30wt%)共混膜在80℃时溶胀度仅为22.5%、26.32%.在室温至80℃范围内,纯SPEEK及共混膜的甲醇透过系数都在10-7cm2.s-1数量级上,远小于Nafion115膜.在饱和湿度下,温度大于90℃时,SPEEK/PES-C(20wt%)共混膜电导率超过Nafion115膜;温度大于110℃时,SPEEK/SPES-C(30wt%)共混膜电导率与Nafion115膜相当,达到0.11S.cm-1.高电导率,低透醇系数以及明显提高了的可使用温度表明该类共混膜有望在DMFC中使用.