十二烷基硫酸钠对膜蒸馏过程影响

膜蒸馏具有较低的操作压力、操作温度以及运行成本等优点,因此在水处理方面有广泛的应用前景。但是膜蒸馏过程中的膜润湿和膜污染现象仍然是阻碍其工业化应用的主要问题。表面活性剂作为一种能显著降低溶液表面张力、改变进料液性质的物质,对膜蒸馏造成的影响值得被研究。基于此,研究了在直接接触式膜蒸馏(DCMD)过程中表面活性剂对不同商业微孔疏水膜造成的影响,选用了一种常见的阴离子表面活性剂十二烷基硫酸钠(SDS)进行实验。结果表明,进料液中SDS浓度的上升会引起更为严重的膜润湿现象,并且所使用的三种商业膜中,双疏膜抗润湿性最强,而PVDF膜最弱。而当Ca~(2+)大量存在于进料液中时,Ca~(2+)与SDS的聚集降低了膜润湿的程度但其在膜表面的沉积造成了严重的膜污染。界面相互作用自由能的计算结果表明Ca~(2+)/SDS与PVDF膜之间的吸引力最大、PTFE膜其次、双疏膜最小,这一结果与膜蒸馏过程中通量变化情况相符。     

膜蒸馏脱盐中膜污染与膜润湿的研究进展

膜蒸馏作为一种脱盐的新兴技术受到广泛关注。然而,因为实际水质组分复杂,可能含有如表面活性剂、油类物质、易结垢盐和有机溶剂等污染物,导致一般疏水膜在长时间运行情况下极易发生膜污染或者膜润湿,最终造成膜通量或截留性能降低。本文首先简述了不同种类的膜污染和膜润湿的特点及形成原因,并分析了膜污染和膜润湿之间的区别和联系。对膜蒸馏过程中膜污染和膜润湿的监测和预测手段进行了简要介绍,最后针对膜蒸馏脱盐过程,重点介绍了近几年国内外预防膜污染和膜润湿的研究进展。研究者一般从污染物与疏水膜的相互作用力着手对疏水膜进行表面改性制备全疏膜和Janus复合膜,避免污染物在膜面的吸附以及抑制表面或孔道润湿。越来越多的研究人员采用致密亲水膜的渗透汽化脱盐来从根本上避免疏水膜带来的润湿。除此之外,对进料液进行预处理也能显著延迟膜的污染和润湿,如混凝/沉淀、膜过滤、煮沸、pH调控等,还可通过改变进料方式、辅助外加磁场等措施控制膜表面局部区域的流体力学状态,减少污染物的附着。适当的膜后处理措施也能恢复膜性能。最后,文章指出了解决膜蒸馏中膜污染和膜润湿的研究方向。     

正渗透膜污染影响因素的研究与分析

以海藻酸钠（ALG）为典型有机污染物,采用TFC FO膜,以水通量下降率和污染阻力作为膜污染的评价指标,探究了正渗透（FO）过程中的膜摆向（FO模式和PRO模式）、原料液（FS）和驱动液（DS）的浓度、原料液中Ca²⁺浓度和pH对FO膜污染的影响规律,并提出适宜的膜清洗方案。结果表明,在PRO模式下,膜污染阻力为3.38×10¹¹m^-1,而在FO模式下仅为3.88×10¹⁰m^-1,表明FO模式污染轻;FS或者DS浓度的增大均会导致污染阻力增大,使得污染更加严重;当FS中不含Ca²⁺和含Ca²⁺浓度分别为1mmol/L和2mmol/L时,相较于初始通量,其通量降低率分别15.40%、18.49%和24.93%,当Ca²⁺浓度从1mmol/L增大到2mmol/L过程中,膜污染阻力增大1.6倍;当FS的pH为4.2、7.0和10.7时,水通量降低率依次增加,分别为14.56%、14.82%和18.78%。分别采用去离子水、pH为3.0的HCl溶液、pH为11.8的NaOH溶液以及十二烷基硫酸钠（SDS,pH=11.0）溶液对膜进行清洗,得到SDS溶液清洗效果较好,通量恢复率可达90.70%。     

SiO2/PVDF渗透膜在高盐废水处理中的性能研究

疏水性差热导率高是制约膜蒸馏在高盐度废水处理领域运用的关键技术参数。为提高膜的疏水性的同时降低膜的导热性能,对自制的SiO₂/PVDF复合膜进行了分子模拟和污染物为Ni²⁺、Co²⁺和Mg²⁺的耐污染实验。通过Materials Studio (MS)软件建立了膜的分子模型。结果表明,羟基含量为40%膜的导热系数最低;采用膜蒸馏+MVR(机械蒸汽再压缩蒸发技术)组合工艺可降低30.61%的处理成本。各污染物与膜表面的非键作用力中,氢键作用能(E_el)为负值且是污染物富集在膜表面的主要作用力。此外,Ni²⁺离子对膜的渗透性能影响最大。     

腐殖酸聚集体对膜蒸馏过程膜污染的作用机理

膜污染是膜蒸馏过程应用于工业水处理中遇到的主要问题之一。选取水体中具有代表性的有机物（腐殖酸）、微溶无机盐（碳酸钙）作为典型污染物,研究有机腐殖酸聚集体对于膜蒸馏过程膜污染进程的影响规律,探讨天然有机物-无机微溶盐混合水体中腐殖酸聚集体对于无机盐结晶过程的控制机理。结果表明：膜蒸馏通量的衰减大致可分为由滤饼层的形成造成的不可恢复部分以及由浓差极化、膜孔“半润湿”而造成的可部分恢复的通量降低。Ca²⁺通过加速腐殖酸分子的聚集过程,使表面负电性降低的腐殖酸聚集体率先吸附在聚偏氟乙烯中空纤维膜内表面,形成有机基质污染层;碳酸钙在有机腐殖酸聚集体的诱导下在膜内表面异相成核,最终成长为稳定的晶体。腐殖酸聚集体为无机盐晶体在疏水性膜内表面的生长提供了异相成核的基础。可通过控制污染水体中有机物的含量控制微溶碳酸钙在膜内表面成核及生长,实现控制其在膜内表面附着进而诱发疏水膜发生亲水化的过程。     

亲水和疏水改性膜的抗结垢和润湿能力的对比

膜蒸馏过程受料液盐度的影响较小，可以处理高矿化度的矿井水，但膜污染和润湿制约其工业化应用。本文首次全面比较了两种商业化的疏水膜，即平板聚四氟乙烯（PTFE）和聚偏氟乙烯（PVDF），以及分别进行亲水和疏水表面改性后制备的PVA-PAA/PTFE和Teflon/PVDF两种复合膜，在直接接触式膜蒸馏（DCMD）中浓缩饱和硫酸钙溶液时的结垢和润湿程度。重点分析了两种基膜和复合膜的结垢和润湿机理，探讨它们在矿井水浓缩中的应用潜力和最佳膜结构。实验结果显示，饱和硫酸钙浓缩过程中，膜表面结垢是主要影响因素，PTFE膜和PVDF膜尽管膜微观结构差别巨大，但抗结垢能力接近；Teflon/PVDF复合膜因其表面有滑移特性而表现出完美的抗结垢性能，PVA-PAA/PTFE复合膜尽管有致密的亲水表面，抗结垢能力并不强。     

膜结晶处理高浓度Na+、Mg2+//Cl——H2O溶液的结晶调控

利用真空膜蒸馏-结晶耦合技术处理多元高盐废水(Na⁺、Mg²⁺//Cl^--H₂O),回收纯水和高品质NaCl晶体产品,考察不同操作温度和不同无机盐离子浓度对膜蒸馏性能和NaCl晶体产品性质调控作用。结果表明随着温度升高导致饱和蒸气压增大,增大了跨膜压差,膜的渗透通量逐渐升高;随着溶液中Mg²⁺浓度的逐渐升高,膜的渗透通量呈下降的趋势,主要是由于水的质量分数下降和溶液黏度增加;膜蒸馏过程中,通过对比实验,分析了疏水微孔膜表面在膜蒸馏操作条件下表面晶体颗粒沉积的程度,证实了使用的中空纤维膜性能稳定,重复使用20次后仍能保持稳定通量;操作温度为65℃时,不同离子浓度的饱和原料液(MgCl₂质量占NaCl和MgCl₂总质量的0%、5.0%和10.0%)得到NaCl晶体产品平均粒径分别为91.04、91.38和122.56 μm,粒度分布的变异系数C.V.值分别为28.78、30.63和36.77,粒径分布集中,表面相貌平整,呈完美的立方体形态,没有团聚现象;同时,膜蒸馏得到的水纯度较高,电导率均小于5 μS?m^-1,采用选择性溶剂乙醇洗涤后的NaCl晶体产品纯度均大于98.15%。综上,通过膜蒸馏过程中渗透通量和膜界面的有效调控,在适宜的操作温度和较低的Mg²⁺含量下,膜蒸馏结晶过程从多元高盐废水(Na⁺、Mg²⁺//Cl^--H₂O)控制分离获得纯度较高、表面形貌完好、粒度均一的NaCl晶体产品。这一研究将为综合治理多元无机高盐废水,实现废水的近零排放和无机盐资源回用开拓新的思路。     

十八烷基硅烷疏水改性PVDF膜的制备及膜蒸馏抗润湿性能

通过相转化法制备的聚偏氟乙烯(PVDF)膜，因致孔剂等添加剂在膜中的残留，导致膜疏水性有限，在膜蒸馏的长时间运行过程中容易被料液污染，失去分离能力。实验采用十八烷基三甲氧基硅烷(OTMS)对碱处理羟基化的PVDF中空纤维膜进行自组装疏水改性，用于提高膜的膜蒸馏抗润湿的能力。通过控制变量探究了OTMS浓度、OTMS自组装时间、热处理温度三个条件对疏水改性膜性能的影响。经过自组装疏水改性后，膜的接触角达到122.5°;在经过12 h质量分数3.5%的氯化钠(NaCl)溶液，2 h质量分数3.5%的NaCl溶液和0.1 mmol/L的十二烷基硫酸钠(SDS)混合溶液膜蒸馏测试中均表现稳定，通量和电导率保持不变，改性膜具有更好的抗润湿能力。     

氧化石墨烯/聚酰亚胺复合膜的制备及其纳滤分离性能的研究

本文以均苯四甲基酸酐(PMDA)、4,4-二氨基二苯醚(ODA)作为原料，在合成过程中加入氧化石墨烯进行掺杂，制备出氧化石墨烯/聚酰亚胺复合膜，并考察了其纳滤分离性能。结果表明，在1.6MPa，膜面流速为0.25m·s^-1，操作温度20℃的条件下，膜通量为46.9L·(m²·h)^-1,Ca²⁺、Mg²⁺截留率分别为91.21%和77.78%；对比相同条件下的纯聚酰亚胺纳滤膜，膜通量提升33.47%,Ca²⁺、Mg²⁺截留率分别提升了13.28%和18.98%。因为氧化石墨烯具有很高的比表面积，并且在表面具有大量的亲水基团等特殊结构，所以通过掺杂可以明显提高聚酰亚胺纳滤膜的分离性能。     

自组装法制备PVDF-SiO2/PVSQ超疏水复合膜及膜蒸馏抗污染性能

采用乙烯基三甲氧基硅烷(VTMOS)对SiO₂疏水改性,通过自组装法,将改性SiO₂接枝在商业PVDF(聚偏氟乙烯)膜表面,使其表面达到超疏水。利用场发射电子显微镜、红外光谱仪、接触角测量仪及毛细流孔径分析仪等仪器对改性前后膜的表面形貌、化学组成、接触角及孔径变化等性能参数进行表征。结果表明,VTMOS不仅对SiO₂疏水改性,还通过自身的水解缩聚反应,生成了规整圆球状的聚乙烯基倍半硅氧烷(PVSQ)微粒,纳米级SiO₂分布于微米级PVSQ表面,在改性膜表面构造了多层次微/纳米粗糙表面,在低表面能疏水基团乙烯基和甲氧基的共同作用下,成功实现了超疏水改性,改性膜水接触角达到159.5°,滚动角降至8.1°。以NaCl、HA和CaCl₂混合溶液为进料液,对商业PVDF膜和改性膜进行了长期直接接触式膜蒸馏(DCMD)实验,探究其抗污染性能。结果表明,改性膜适用于长期DCMD实验,并表现出比商业PVDF膜更稳定的通量,截盐率始终大于99.99%,具有良好的稳定性和抗污染性能。     

膜蒸馏脱盐过程膜润湿的研究进展

膜蒸馏（MD）适合在偏远地区小规模制备淡水,有脱盐率高、接近常压操作、可利用太阳能等优势。但MD膜润湿影响了装置的运行稳定性,是制约MD脱盐应用的重要因素之一。本文介绍了MD膜润湿的评价方法,包括测定透水压力、临界膜孔润湿深度及可视化在线监测膜润湿进程等;简述了膜污染、MD操作变量、膜蒸馏形式及不同结垢晶体各因素对膜润湿的影响;从防垢和强化通量、掌握合适的膜清洗周期、物理干预及提升MD膜性能等方面分析了抑制膜润湿的措施;并分析了一些脱盐实验时间较长的MD膜润湿情况;指出具有自清洁性的光催化膜及防垢性能更强的双疏膜和Janus膜,具有抑制MD膜润湿的巨大潜力。本文有助于对脱盐过程中MD膜润湿的预测和有效控制。     

Bottlenecks and recent improvement strategies of ceramic membranes in membrane distillation applications: A review

Ceramic membranes have received more attention currently from researchers in membrane distillation (MD) applications due to their outstanding properties. However, despite their superior mechanical, thermochemical stability, and resistance to harsh operating conditions, several bottlenecks still limit their applications in MD. Although there are several published articles on ceramic membranes in MD, the uniqueness of this review lies in the fact that it discusses the critical bottlenecks that significantly affect the performance of ceramic membranes in long-term operation and limit their scale-up to commercial MD applications. Furthermore, recent advances, strategies, and techniques to mitigate these limitations have also been discussed. A discussion on high ceramic membrane fabrication costs and mitigation strategies using alternative low-cost ceramic materials to erstwhile conventional ceramic materials has been presented. In addition, the inherent problems of the brittleness and wetting/fouling of ceramic membranes and recent advances in strengthening ceramic membranes and fouling/wetting control via the development of superhydrophobic and omniphobic ceramic surfaces in MD have been addressed. Consequently, technical bottlenecks that still exist despite recent development in ceramic membranes for MD applications have been highlighted and future research direction in developing robust ceramic membranes in MD applications has been elaborated.     

直接接触式膜蒸馏过程的膜曝气强化

针对直接接触式膜蒸馏（direct contact membrane distillation,DCMD）过程存在的膜通量小及膜污染问题,设计了一种新型结构的膜蒸馏组件。以蔗糖溶液为处理液,考察了膜组件装填密度Φ、膜曝气量q、蔗糖浓度c与温度T₀对DCMD过程的影响。结果表明：随着Φ、q的增加,DCMD过程的膜通量先增大,后逐渐降低,Φ、q均存在最优值;随着c的增加,膜通量逐渐降低;随着T₀的增加,膜通量增大;对c为30%（mass）的蔗糖溶液进行DCMD法处理330 min时,膜曝气可使DCMD的初始膜通量J_initial提升24.7%、膜通量衰减率ΔJ降低55.0%,维持高膜通量的连续运行时间t₀延长4倍。主要原因是膜曝气强化了DCMD过程的传热传质,进而强化过程的分离性能;有效控制了DCMD过程的浓差极化,进而延缓过程的膜污染进程。研究结果有利于推进DCMD的工程化应用。     

Influence of flocculant polyacrylamide on concentration of titanium white waste acid by direct contact membrane distillation

Effort has been made to investigate the concentration of titanium white waste acid (TWWA) by direct contact membrane distillation (DCMD) and the focus is the influence of polyacrylamide (PAM) on membrane wetting and fouling. It was found that the presence of PAM in feed reduced membrane flux and retarded wetting development, even though its level in feed of H₂SO₄ solution was only 0.0002 wt%. The difference between the tests using pure water and neat PAM aqueous solution, respectively, as feed also indicated the above effect registered with PAM. AFM results showed that the addition of PAM in feed solution changed the membrane shell surface morphology. However, conclusive proof of the PAM existence in membrane cross-section and inner surface was not obtained, probably due to its low concentration in feed solution. Two approaches were tried to recover membrane flux. In comparison with operation w/o any treatment, HCl solution rinsing did not lead to obvious improvement in membrane flux recovery, while rinsing combined with gas purge has clearly delayed the degradation in acid concentration factor. Nevertheless, even the latter could not ensure long term stability. High tortuosity and low hydrophobicity of the membranes used were suggested as underlying causes and should be addressed in the future.     

Impact of fouling,cleaning and faecal contamination on the separation of water from urine using thermally driven membrane separation

In this study, membrane distillation is evaluated as a technology for non-sewered sanitation, using waste heat to enable separation of clean water from urine. Whilst membrane fouling was observed for urine, wetting was not evident and product water quality met the proposed discharge standard, despite concentration of the feed. Fouling was reversible using physical cleaning, which is similar to previous membrane studies operating without pressure as the driving force. High chemical oxygen demand reduction was achieved following faecal contamination, but mass transfer was impeded and wetting occurred which compromised permeate quality, suggesting upstream intervention is demanded to limit the extent of faecal contamination.     

Fouling evaluation on membrane distillation used for reducing solvent in polyphenol rich propolis extract

Membrane distillation (MD) has not been widely studied in the concentrate of phenolic rich solution in comparison to osmotic distillation.In this work,the potential of MD to reduce solvent in the polyphenol rich propolis extract was further investigated.Polyvinylidene fluoride (PVDF) membranes were engineered with the smaller pore size for the less hydrophobic surface in order to avoid wetting,allowing only the solvent vapor to be transferred from the warm feed into the cold permeate.All the membranes exhibited more than 95％ rejection of phenolic and flavonoid compounds.Although the hydrophilic membranes exhibited less fouling,they displayed a lower flux than the hydrophobic membrane due to the hindrance in the wetted pores.The hydrophobic membrane was seriously fouled by the phenolic acid as shown in the Fourier transform infrared spectroscopy spectrum.Pore plugging occurred on these hydrophobic membranes as confirmed in the scanning electron microscope images.     

Innovative hydrophobic/hydrophilic perfluoropolyether (PFPE)/polyvinylidene fluoride (PVDF) composite membrane for vacuum membrane distillation

Though membrane distillation (MD) has gained more and more attention in the field of desalination, the wetting phenomenon was still a non-negligible problem. In this work, a method combined dip-coating and UV in situ polymerization for preparing hydrophobic/hydrophilic perfluoropolyether (PFPE)/polyvinylidene fluoride composite membranes. This composite membrane consisted of a top thin hydrophobic coating layer and hydrophilic substrate membrane. In terms of anti-wetting properties, contact angle and liquid entry pressure of all composite membranes (except for those based on 0.45 μm) exceeded 160° and 0.3 MPa, respectively. In particular, the desalination performance was tested in vacuum membrane distillation tests by feeding 3.5% (mass) saline solution (NaCl) at 60 ℃. The composite membranes with larger support pore size and lower PFPE content had higher membrane distillation flux. And for stability tests (testing the 0.22 μm membrane coated by 5% (mass) PFPE), the highest MD flux 29.08 kg·m^-2·h^-1 and stable salt rejection (over 99.99%) during the period. Except that, the effects of coating material concentration and pore sizes of substrate membrane were also investigated for surface morphology and topography, porosity, mechanical strength and pore size characteristics. This work provided a simple and effective alternative to prepare excellent hydrophobic composite membranes for MD applications.