超滤过程膜污染控制技术研究进展

探讨了超滤过程中的浓差极化和膜污染形成的机理以及影响膜污染的因素 ,综述了预防和控制膜污染的各种技术 ,包括膜材及孔径的选择、膜组件的设计、原料的预处理、膜过程的强化及膜的清洗等技术。指出开发新型实用的耐污染膜和能耗少、寿命长、抗污染的膜组件 ,对膜过程工艺进行优化控制 ,开发高效的在线清洗技术和经济便利的离线清洗技术等是尚待攻克的课题。     

弹状流对陶瓷膜超滤葡聚糖水溶液的影响

为降低膜污染和浓差极化需维持较高膜面流速,能耗较高。将气升式外循环引入膜过程,可有效降低浓差极化和能耗。实验考察了曝气量对渗透通量的影响,当曝气量为400 L·h^-1时,与相同液速条件下单相流错流过滤相比较,膜通量提升87%;进一步增大曝气量,膜通量增加趋势变缓。对气升式膜过滤过程的水力学特性进行了研究,在弹状流条件下,气液两相流可有效提高膜面剪切力,增强膜面传质。在较低流速下,曝气可有效降低膜污染阻力,提高膜通量。结合气液两相流理论和膜过滤阻力模型,分析了弹状流提升膜通量的机理。     

Characterization of mixed matrix membranes by adsorption and fractal analysis

ABSTRACT

CO₂, CH₄ and N₂ adsorption properties of KFI- and RHO-polyvinyl acetate mixed matrix membranes (MMMs) were determined. A comparison was made between experimental and calculated adsorption capacities of the membranes. The fractal dimensions of the membranes were calculated from CO₂ adsorption data. A common discrepancy existed between experimental and calculated adsorption capacities of MMMs, which may be rationalized by the presence of an interphase between filler and polymer phases. The higher fractal dimension of KFI-polyvinyl acetate MMM, compared to RHO-polyvinyl acetate MMM indicated higher size sensitivity and thus an additional advantage for the adsorption of smaller molecules, such as CO₂.     

聚偏氟乙烯超滤膜亲水改性研究进展

膜污染会缩短超滤膜的使用寿命,增加由于水力清洗、化学清洗以及膜组件更换而产生的费用。为减少运行成本,有必要对膜污染加以控制。膜污染与原水中污染物的性质和膜本身的性质密切相关。亲水性膜具有水通量高、抗污染性能好的特点,因而提高超滤膜的亲水性是提高膜的水通量和控制膜污染的重要方法之一。简要介绍了具有良好化学稳定性、耐辐射性、耐热性的聚偏氟乙烯膜的表面亲水改性和共混亲水改性的研究进展,指出通过不同的改性方式,聚偏氟乙烯膜都能够实现亲水性的增强。     

Long‐term study of CO2 absorption by PVDF/ZSM‐5 hollow fiber mixed matrix membrane in gas–liquid contacting process

In order to fabricate hollow fiber mixed matrix membrane (HFMMM) for long‐term CO₂ absorption process, ZSM‐5 (Zeolite Socony Mobil–5) zeolite was modified using hexadecyltrichlorosilane for increasing hydrophobicity and then added to the polyvinylidene fluoride (PVDF) spinning dope. The in‐house made HFMMMs were characterized in terms of gas permeance, overall porosity, average pore size, effective surface porosity, surface roughness, mechanical stability, and wetting resistance. The morphology of the HFMMMs was studied using SEM. The cross‐sectional SEM images indicated that the membrane structure has changed from sponge‐like to finger‐like by ZSM‐5 loading. The surface roughness increased by increasing ZSM‐5 concentration in the spinning dope. The HFMMM spun from the spinning dope with 0.5 wt % of ZSM‐5 zeolite showed that the CO₂ absorption flux decreased 18.9% in the initial 115 h of the operation and then the absorption flux remained constant until the end of the operation. For plain PVDF HFM the absorption flux decreased 36% from the initial value in the first 15 h of the experiment. Thus it could be concluded that the long term stability of HFM was improved by the incorporation of ZSM‐5. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44606.     

Reduced-order modeling of flow and concentration polarization in membrane systems with permeation

Modeling of concentration polarization (CP) is important to ensure a successful membrane system design. Although computational fluid dynamics (CFD) remains a common approach to study CP, it usually requires a long computational time to investigate a short simulated time in membrane systems. In this work, we proposed a reduced-order model to predict CP in membrane systems with permeation. We modify Berman's velocity profile and incorporated it to the reduced-order model of the mass-transfer equation. The proposed model shows excellent agreement with CFD results, while offering a reduction of two orders of magnitude in computational time. We also validate the model with published experimental data and demonstrate that the model can predict permeate flux in close proximity under various operating conditions. The proposed model offers an attractive alternative to solving the full Navier–Stokes and mass-transfer equations, and opens the possibility to further investigate various approaches to reduce concentration polarization.     

温敏性PVDF/PGS-g-PNIPAM纳米复合超滤膜的制备和性能

通过化学接枝法将聚(N-异丙基丙烯酰胺)(PNIPAM)接枝聚合在凹凸棒石(PGS)纳米纤维表面,制备了系列接枝率的温敏性PGS-g-PNIPAM纳米颗粒,将其与聚偏氟乙烯(PVDF)共混制备温敏性纳米复合超滤膜,深入研究PNIPAM接枝率对膜结构和性能的影响。结果表明,凹凸棒石表面PNIPAM接枝率随溶液中NIPAM单体浓度增大而增加;PGS-g-PNIPAM使复合膜中PVDF晶核变小,数目增多,膜更为疏松多孔,PVDF/PGS-g-PNIPAM膜的平均孔径在20 nm左右,膜的平均孔径和最大孔径均随凹凸棒石表面PNIPAM接枝率的增加而增大;PVDF/PGS-g-PNIPAM膜具有温敏性,温敏开关系数随PNIPAM接枝率的增加先增强后减弱,当接枝率为21.33%时膜温敏开关系数最大,达到1.51,膜渗透通量也最大,对牛血清白蛋白具有良好的截留和抗污染性能。     

Determination of membrane areas for ultrafiltration processes

For batch mode ultrafiltration processes a numerical method for calculating membrane area has been devised with flux predicted from Flemmer's model. Erythromycin broth filtrate was used as a model fluid. Experiments at a 20 dm³ scale were used to estimate the parameters involved in Flemmer's equation, from which membrane areas appropriate for operations of 80 metric tons were calculated. Factors such as rejection, concentration ratio, etc, which affect the membrane size for batch operation, are discussed. The calculated results were consistent with experimental data at the 100 dm³ scale. For continuous operation equations for calculating membrane areas have also been established. The minimum membrane area was calculated at the optimum concentration ratios of each stage, usually their values were different at each stages. Comparison between batch and continuous mode in the context of the membrane area required is also discussed. The method could be applicable to other ultrafiltration operations. © 2001 Society of Chemical Industry     

Facile preparation of Cu(I) impregnated MIL‐101(Cr) and its use in a mixed matrix membrane for olefin/paraffin separation

Cu(I) impregnated MIL‐100(Cr) [denoted Cu@MIL‐101(Cr)] is fabricated by a facile method and utilized in mixed matrix membranes (MMMs) for propylene/propane separation. Cu(I) is prepared from a CuCl₂ solution via mild reduction process using sodium sulfite as the reducing agent. The filler is incorporated into a polystyrene‐b‐polybutadiene‐b‐polystyrene (SBS) block copolymer matrix to form MMMs. As a result, both the permeability and selectivity of propylene/propane are improved after Cu(I) impregnation. The best performance is obtained for SBS/Cu@MIL‐101(Cr) MMM, and these values represent 17% and 54% improvements compared to those of SBS/MIL‐101(Cr) MMM, respectively. This result is attributed to the π‐complexation of the loaded Cu(I) by propylene gas, indicating that Cu@MIL‐101(Cr) with internal Cu(I) and a high pore volume acted as an effective filler to aid propylene/propane separation. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46545.     

膜厚度和流动状况对渗透蒸发过程的浓差极化影响

浓差极化对渗透蒸发过程的渗透速率和分离因子有一定负面影响。文中利用渗透蒸发过程中的分步阻力传质模型分析浓差极化,以含乙醇质量分数2%的乙醇/水为进料体系,观察进料流速对渗透蒸发过程中分离因子和通量的影响。分别估算了边界层阻力和膜阻力以及流速对边界层阻力的影响,并考察了膜厚度对浓差极化和分离因子的影响。     

膜分离中的浓差极化现象及其减弱措施

分析了膜分离中的浓差极化现象的产生原因,并提出与此对应的减弱措施.     

Pervaporative enrichment of 2,3‐butanediol from its mixture with 1‐butanol using a polydimethylsiloxane and ZSM‐5 mixed matrix membrane: Effects of ethanol as a by‐product

A ZSM‐5 filled polydimethylsiloxane membrane with 44.4 wt.% zeolite loading was used in the pervaporative removal of 1‐butanol from its mixtures with 1‐butanol. A small quantity of ethanol was added to the feed as a by‐product to test the response of the membrane. It was found that the permeation behaviour of other feed components was changed and membrane selectivity decreased. This change was attributed to the frequently‐observed inter‐component coupled transport in multi‐component feed systems. The impact of ethanol on recovery of 2,3‐butanediol was evaluated using a simulated continuous operation, which enriched 2,3‐butanediol to 99.5 wt.% from a feed containing 5 wt.% 2,3‐butanediol and less than 1.0 wt.% ethanol. It was observed that membrane selectivity improves as ethanol concentration decreases in the stream due to its preferential removal. The final recovery of 2,3‐butanediol was not significantly reduced as the concentration of ethanol was below 1.0 wt.%. © 2011 Canadian Society for Chemical Engineering     

Removal of Ni(II) ions from wastewater by micellar enhanced ultrafiltration using mixed surfactants

Ni(II) ions were removed from aqueous waste using micellar enhanced ultrafiltration (MEUF) with a mixture of surfactants. The surfactant mixture was the nonionic surfactant Tween 80 (TW80) mixed with the anionic surfactant sodium dodecyl sulfate (SDS) in different molar ratios ranging from 0.1–1.5. The operational variables of the MEUF process such as pH, applied pressure, surfactant to metal ion ratio and nonionic to ionic surfactant molar ratio (α) were evaluated. Rejection of Ni and TW80 was 99% and 98% respectively whereas that for SDS was 65%. The flux and all resistances (fouling resistance, resistance due to concentration polarization) were measured and calculated for entire range of α respectively. A calculated flux was found to be declined with time, which was mainly attributed to concentration polarization rather than resistance from membrane fouling.     

A model of ceramic membrane fouling during heavy oil ultrafiltration

Fouling of asymmetric, single tube ceramic membranes during ultrafiltration of Cold Lake heavy oil, is described by a pore restriction fouling model that predicts reduced permeate flux but increased asphaltene rejection with increased time-on-stream. Application of the model to experimental data showed that a 2nd-order rate of asphaltene adsorption/deposition within the membrane pores, described the data better than a 1st-order model. The asphaltene molecular radius, estimated as a parameter of the model, was in the range 3.8 - 14.2 nm, depending on the membrane pore diameter. These values are in good agreement with previously published estimates of asphaltene particle size, determined using different experimental techniques.     

Poly(vinyl alcohol)/ZIF‐8‐NH2 mixed matrix membranes for ethanol dehydration via pervaporation

Ethanediamine‐modified zeolitic imidazolate framework (ZIF)‐8 particles (ZIF‐8‐NH₂) is synthesized and incorporated in the poly(vinyl alcohol) (PVA) matrix to fabricate novel PVA/ZIF‐8‐NH₂ mixed matrix membranes (MMMs) for pervaporation dehydration of ethanol. The PVA/ZIF‐8‐NH₂ MMMs exhibit enhanced membrane homogeneity and separation performance because of the higher hydrophilicity and restricted agglomeration of the particles, as compared to corresponding MMMs loaded with unmodified particles. The effect of ZIF‐8‐NH₂ loading in the MMMs is studied and the MMM with a 7.5 wt % ZIF‐8‐NH₂ loading shows the best pervaporation performance for ethanol dehydration at 40°C. Various characterization techniques (Fourier transform infrared, scanning electron microscope, contact angle, sorption test, etc.) are used to investigate the MMMs loaded with ZIF‐8 and ZIF‐8‐NH₂ particles. The impact of operation conditions on pervaporation performance is also performed. The performance benchmarking shows that the MMMs have superior separation factors and comparable flux to most other PVA hybrid membranes. © 2016 American Institute of Chemical Engineers AIChE J, 62: 1728–1739, 2016     

超滤与泡沫分离内耦合应用于表面活性物质浓缩分离的实验研究

Membrane separation and foam separation are widely used separation techniques.To make use of their advantages,membrane separation and foam separation were integrated to dispose waste water with low concentration of linear alkylbenzene sulfonate（LAS）.A method of forcing bubbles through a single hollow fiber ultrafiltration tube was put forward to study the separation efficiency of the integrated process.The effects of pressure,gas-liquid ratio and LAS concentration on the separation efficiency were investigated.Under the conditions of pressure 0.03—0.1 MPa,gas-liquid ratio 0—0.9,and LAS concentration 0—70 mg·L^-1,the membrane permeate flux was raised from 26.5 to 38.6 L·m^-2·h^-1,increased by 48.6%,and the retention rate was raised from 37.0% to 64.9%,increased by 75.5%.The results show that the integrated process can reduce the concentration polarization and membrane fouling.Moreover,this method reduces the back-mixing of foam separation and increases the concentration of bulk liquid phase for foam separation.Therefore,the integrated separation promotes mass transfer and improves separation efficiency.     

抗菌超滤膜的研究进展

为了改善超滤膜的使用寿命,其抗菌性能研究已成为近几年研究的热点。主要从膜表面改性和膜材料改性2个方面综述了抗菌超滤膜的制备方法,重点介绍了表面涂覆、表面接枝和共混法这3种常用改性方法的特点以及改性后膜的抗菌效果,并指出制备抗菌超滤膜所存在的问题,以及今后的发展方向。     

ZIF-L/PDMS混合基质膜蒸气渗透耦合发酵强化乙醇生产效率的研究

蒸气渗透（VP）膜分离不存在膜污染风险,在生物乙醇生产中具有广阔的应用前景。将聚二甲基硅氧烷（PDMS）膜和以二维沸石咪唑骨架（ZIF-L）为填充基质制备的PDMS（ZIF-L/PDMS）混合基质膜,分别用于VP膜分离与菊粉水解液发酵制乙醇过程的耦合,分析了二者在耦合过程中的分离性能和发酵性能。探究了不同膜分离方式、不同类型膜及操作条件对膜分离性能的影响。实验结果表明,当料液浓度为5%（质量）、蒸气循环流量为1.5 L·min^-1时,ZIF-L/PDMS混合基质膜的VP性能高于渗透汽化（PV）,归一化总通量达到1148.78 g·m^-2·h^-1,分离因子高达19.14,显著提升了乙醇分离性能。ZIF-L/PDMS混合基质膜用于VP耦合发酵,实现了耦合过程的高渗透性和乙醇选择性,与文献报道相比,乙醇移除效果最优,乙醇产率和时空产率分别达到0.421 g·g^-1、3.07 g·L^-1·h^-1,两个指标明显高于单独发酵,极大地提高了乙醇生产效率。因此,ZIF-L/PDMS混合基质膜在原位分离发酵乙醇方面具有很大的应用潜力。