纳滤膜技术及其应用的研究进展

随着膜技术的发展,20世纪80年代出现的纳滤膜弥补了反渗透与超滤之间的空白。纳滤膜(nanofiltration membrane,NF)又称“疏松型”反渗透膜。通常情况下,膜的截留相对分子质量界限为200~1 000。与截留相对分子质量相对应的膜孔径为1~3 nm,故将这类膜称为纳滤膜。纳滤膜可以截留糖类等低相对分子质量有机物和高价无机盐(MgSO4等),但对单价无机盐的截留率低(仅为10%~80%),具有相当大的透过能力。由于单价盐可以自由透过纳滤膜,使得膜两侧因离子浓度不同而造成的渗透压差远远低于反渗透膜。在相同通量条件下,纳滤膜所要求的驱动压力比反渗透膜要低得多。一般纳滤的操作压力为0.5~1.5 MPa。由于纳滤膜的这种独特分离性能,确定了它在水软化和低相对分子质量有机物纯化浓缩的地位。此外,纳滤膜能有效去除许多中等相对分子质量溶质,如消毒副产物的前驱物、残留农药和某些色素等,因而在水净化处理和脱色中得到广泛应用。     

饮用水深度净化工艺现场对比试验

考察了实际生产规模的臭氧粒状活性炭工艺以及小型超滤、纳滤、反渗透膜法两种典型饮用水深度净化工艺的处理效果。试验结果发现臭氧活性炭工艺具有优良、稳定的去除有机污染物功能,而孔径较小的活性炭纤维除污染效果并不好,臭氧氧化出水、超滤出水再用压缩活性炭进行吸附处理对有机物的去除效率要比直接处理原水高。超滤膜除有机物效率不高,而反渗透和纳滤膜在较好地去除水中有机物的同时,也去除了水中绝大部分无机物,出水有机物和无机物浓度都比较低。     

水中有机污染物的分子量分布特征对纳滤膜透水性能影响的试验研究

使用分级分离膜对纳滤膜系统的原水、浓缩水、透过水以及预处理透过水进行了分子量分布的分析测定 ,发现水的回收率为 90 %时 ,分子量 1万～ 10万的物质附着于纳滤膜的表面 ,并且随着回收率的降低 ,膜表面的污染物向高分子量变化。用TOC浓度相同而分子量分布不同的原水进行了透水试验 ,结果表明 ,造成纳滤膜污染的根本原因是原水中有机污染物的分子量分布特征 ,而不是单纯的原水浓度     

锰砂/石英砂滤池与纳滤膜组合工艺去除水中砷的研究

采用锰砂/石英砂滤池与纳滤膜组合工艺处理含砷水,考察锰砂/石英砂、纳滤膜(NF90、HL)、锰砂/石英砂滤池与纳滤膜组合工艺对水中砷的去除效果.结果表明,三价砷(As(Ⅲ))和五价砷(As(Ⅴ))经锰砂/石英砂过滤后能得到很好的去除,原水砷浓度250 μg/L,出水砷浓度小于50μg/L;纳滤膜对五价砷(As(Ⅴ))的去除能力很高,能达到90%以上,但是对三价砷(As(Ⅲ))的去除率不理想,为40%～60%;锰砂/石英砂复合滤池与纳滤膜组合工艺对水中砷有很好的去除效果,出水砷浓度均小于10μg/L,是理想的饮用水除砷方法.     

纳滤和反渗透技术在高含盐地下水中的应用及比较研究

J市地下水无机盐污染物超标,常规工艺难以有效处理。为保障居民用水品质,开展以纳滤和反渗透为核心的膜分离技术中试和扩展小试研究。结果表明:使用超滤作为预处理工艺能有效保证纳滤和反渗透工艺的进水水质;纳滤和反渗透工艺能有效去除水中的TDS、总硬度、硫酸盐、氟化物、UV_(254)和DOC,除氟化物外去除率均在95%以上,且纳滤和反渗透工艺运行稳定,投加阻垢剂后无明显膜污染;为提高经济性,可将处理水与原水掺混供水,掺混比为38%,掺混后供水水质达标;通过技术经济分析,结合当地水质情况,纳滤工艺更适合作为改造的核心工艺。     

纳滤膜对饮用水中可同化有机碳的去除效果

考察了纳滤膜对饮用水中有机物和可同化有机碳(AOC)的去除效果。对纳滤膜进水和出水进行了AOC的相对分子质量分布测定,分析AOC和有机物相对分子质量分布间的关系,探讨纳滤膜去除AOC的机理。结果表明,纳滤膜能有效地去除TOC和UV254,去除率均高达95%以上;在不同季节,自来水中AOC浓度有显著的变化,其中AOCP17约占AOC总量的60%~70%;纳滤膜对饮用水中AOC的去除率约为60%,其去除效果受到筛分效应和电荷效应的双重影响。AOC多与相对分子质量小于1000的有机物有关。     

低压纳滤膜用于微污染地表水深度处理的中试研究

采用低压纳滤中试装置深度处理微污染地表水源水。探讨了其中纳滤膜的截留性能和膜污染情况。中试结果表明DF30纳滤膜呈现出高天然有机物截留特性,同时保留部分对人体有益的钙镁离子。TOC、硫酸根、电导率和硬度平均去除率分别为94%、87%、27%和43%。纳滤膜对微量有机物平均去除率为65%。膜表征的结果表明膜污染的主要污染物为多糖和蛋白质。污染层ATP含量为20.3ng/cm~2,表明存在中等程度的生物污染。在碱性条件下采用EDTA+SDS的清洗方式能将膜通量恢复至初始通量的90%,有效减缓膜污染。纳滤运行成本约为0.36元/m~3,具有良好的经济性。     

全膜深度处理工艺处理太湖水的中试研究

采用超滤-纳滤(UF-NF)全膜工艺处理东太湖水,通过中试考察全膜工艺对水中各种污染物的处理效能。试验结果表明,超滤预处理能充分保证纳滤的稳定运行,试验工艺处理浊度、COD_(Mn)、TOC、UV_(254)、氨氮、藻密度和叶绿素a的去除率分别为99.93%、89.33%、62.33%、93.72%、82.1%、99.67%和98.32%。工艺对水中的TDS和电导率的去除率为43%。三维荧光和有机物特性分析表明,原水中有机物构成以芳香蛋白类物质、溶解性微生物代谢产物和小分子有机物为主,全膜工艺去除效果优异。     

超滤-纳滤双膜工艺深度处理南四湖水中试研究

针对南四湖水源水中高有机物、高含盐量的特点,采用超滤-纳滤工艺进行了中试研究,对比分析了2种纳滤膜(H膜、G膜)的处理效果。试验结果表明:超滤-纳滤双膜工艺可有效应对水源中存在的有机物和无机盐污染问题,2种纳滤膜对无机盐离子去除率在90%以上,H膜与G膜对DOC的去除率的分别为98.7%和81.6%,H膜出水水质优于G膜。相同压力和温度下G膜的通量要高于H膜,同时单位产水量的能耗G膜也要低于H膜;污染后的纳滤膜进水端主要是有机物污染,出水端主要是无机盐结垢。化学清洗可将膜通量恢复至初始通量的90%以上,但清洗后的膜面仍然存在微量的有机物和无机盐结垢,这是形成纳滤膜不可逆污染的主要原因。     

臭氧-生物活性炭-纳滤膜深度处理饮用水试验研究

采用臭氧-生物活性炭-纳滤工艺去除城市管网供水中的污染物,使其达到饮用净水水质标准.研究表明:在臭氧投加量为3～4 mg/L,接触时间8～10 min,生物活性炭罐滤速3～4 m/s的运行条件下,臭氧-生物活性炭预处理能够大量去除原水中的污染物,保证纳滤工艺的正常运行;纳滤膜在操作压力0.7～0.8 MPa,膜通量为27.3 L/(m2·h)的条件下,既能去除无机污染物,又能够保证一些对人体有益的离子不被完全截留;且能够有效去除原水中的TOC、AOC、CODMMn、色度、浊度及细菌等,确保饮用水的安全性和生物稳定性.     

纳滤膜和低压反渗透膜去除水中氟的对比研究

通过采用NF/RO膜技术去除水中氟离子的试验研究,探讨了膜回收率、操作压力、水的pH、进水含盐量以及运行时间等参数对NF/RO膜除氟效果的影响.试验中确定NF/RO膜的最佳回收率均为15%.结果表明:在相同操作条件下(0.16～0.21 MPa),RO的膜通量是NF的1/2左右,而其F-去除率比NF高2%～15%;水的pH影响NF/RO膜对氟的去除效果,pH越高,膜对氟的去除率越高;随着进水含盐量的增加,NF/RO膜对F-的去除率下降;随着运行时间的增加,RO膜等对F-的去除率基本保持不变,NF膜下降明显.建议RO膜除氟最低压力应高于0.2 MPa;膜法除氟应尽量在弱碱性环境中操作.     

Comparison of SAR (sodium adsorption ratio) between RO and NF processes for the reclamation of secondary effluent.

Secondary effluent reclamation and reuse has been considered as an alternative for agricultural irrigation water. Whilst all constituents in the reclaimed wastewater could affect plant growth and soil characteristics, the most important parameters for agricultural irrigation are salinity and SAR (Sodium Adsorption Ratio). Salinity affects the availability of crop water and sodium causes clay soils to disperse. Membrane technologies, especially NF (Nano-Filtration) and RO (Reverse Osmosis), have played in a key role reclaiming the secondary effluent. RO can remove monovalent and divalent cations simultaneously. However NF processes reject preferably divalent cations and most monovalent ions are allowed to pass through the NF membranes. This could make them have different SAR values for both NF and RO processes. Therefore the primary objective of this study is to examine if the SAR values of the reclaimed water could be changed while they undergo NF and RO processes. The measured SAR values of the secondary effluent, NF permeate, and RO permeate were 1.78, 4.67, and 0.72 respectively. The SAR value after NF (4.67) increased to more than twice that of the feed solution, whereas the SAR of the RO permeate decreased to 0.72. In general, the higher SAR the water has, the greater risk the soils have. Although the SAR value after NF was within the safe range, this increased SAR value will affect permeability of soil, thus limiting the reclaimed wastewater use for as agricultural irrigation water. Consequently, when the NF system is used for the reclamation of the secondary effluent, SAR has to be examined first because potentially it tends to increase the SAR value.     

RO brine treatment and recovery by biological activated carbon and capacitive deionization process

The generation of brine solutions from dense membrane (reverse osmosis, RO or nanofiltration, NF) water reclamation systems has been increasing worldwide, and the lack of cost effective disposal options is becoming a critical water resources management issue. In Singapore, NEWater is the product of a multiple barrier water reclamation process from secondary treated domestic effluent using MF/UF-RO and UV technologies. The RO brine (concentrates) accounts for more than 20% of the total flow treated. To increase the water recovery and treat the RO brine, a CDI based process with BAC as pretreatment was tested. The results show that ion concentrations in CDI product were low except SiO2 when compared with RO feed water. CDI product was passed through a RO and the RO permeate was of better quality including low SiO2 as compared to NEWater quality. It could be beneficial to use a dedicated RO operated at optimum conditions with better performance to recover the water. BAC was able to achieve 15-27% TOC removal of RO brine. CDI had been tested at a water recovery ranging from 71.6 to 92.3%. CDI based RO brine treatment could improve overall water recovery of NEWater production over 90%. It was found that calcium phosphate scaling and organic fouling was the major cause of CDI pressure increase. Ozone disinfection and sodium bisulfite dosing were able to reduce CDI fouling rate. For sustainable operation of CDI organic fouling control and effective organic fouling cleaning should be further studied.     

几种膜组件在管道直饮水处理系统中应用对比

膜处理是管道直饮水处理工艺的核心,介绍了微滤膜(MF)、超滤膜(UF)、纳滤膜(NF)、反渗透膜(RO)四种膜在管道直饮水处理系统中应用的对比,内容包括基本性能、去除杂质能力、工作压力以及出水电阻率等。结果显示,相比于其他三种膜,纳滤膜(NF)在直饮水处理工艺应用更具优势。     

Recent operational experiences of FILMTEC NF270 membrane in Europe

Nanofiltration (NF) is an attractive technology for potable and industrial water treatment because NF operates between ultrafiltration (UF) and reverse osmosis (RO) membranes. NF is designed to remove a high percentage of organic contaminants (humic acids, pesticides, color bodies) while passing a medium to high percentage of salt. Compared to UF membranes, the NF product water quality is significantly better; compared to comparable RO treatment systems NF systems require lower operating pressures. Due to these features, NF is increasingly used in a broad range of water treatment applications. The general applications include softening, as well as color, organics and micro-organism removal. DOW FILMTEC NF270-400 is one the most frequently used elements in water treatment and this paper presents examples of three recent NF270-400 installations in Europe. The first two plants, Eupen and Stembert, are located in Belgium and produce potable water from surface water. The third one is a Scandinavian plant which purifies groundwater for a brewery and soft drink production. The presented operation results prove NF to be a highly competitive technique for low cost water treatment.     

Review on the fate of organic micropollutants in wastewater treatment and water reuse with membranes

A brief review of the fate of micropollutants in membrane-based wastewater treatment due to sorption, stripping, biological degradation/transformation and membrane separation is discussed, to give an overview of these technologies due to the growing importance for water reuse purposes. Compared with conventional activated sludge treatment (CAS) micropollutant removal in membrane bioreactor (MBR) is slightly improved due to complete suspended solids removal and increased sludge age. For discharge to sensitive receiving waters advanced treatment, such as post-ozonation or activated carbon adsorption, is recommended. In water reuse plants nanofiltration (NF) and reverse osmosis (RO) efficiently reject micropollutants due to size exclusions as well as electrostatic and hydrophobic effects reaching potable quality. To remove micropollutants fully, additionally post-ozone or the addition of powdered activated carbon (PAC) have to be applied, which in parallel also reduce NDMA precursors. The concentrate has to be treated if disposed to sensitive receiving waters due to its high micropollutant concentration and ecotoxicity potential. The present review summarizes principles and capabilities for the most important membrane-based applications for wastewater treatment, i.e. porous membranes in MBRs (micro- or ultrafiltration) and dense membrane applications (NF and RO) for water reuse.     

组合膜分离技术资源化处理印染废水工艺的研究

为解决印染废水的资源化处理问题,针对实际印染废水研究了以超滤和纳滤膜分离技术为核心的印染废水处理及回用工艺在工程上的可行性。实验结果表明:还原染料废水采用超滤系统处理,膜出水水质即能够满足印染厂内回用水质要求;活性染料废水通过纳滤浓缩能够获得较好的染料回收效果。采用双膜膜分离系统(UF+NF)能够使两种染料废水的污染物均得到明显去除,还原性染料废水的总悬浮物、COD、浊度和色度的去除率达到了100%、95.21%、92.86%和100%;活性染料废水上述各项指标去除率达到100%、82.85%、98.46%和99.43%。双膜膜分离系统适用于工业印染废水处理及染料回收,是资源化处理印染废水的发展方向。     

低温低浊水絮凝工艺的数值模拟与响应面优化试验研究

为探究微涡流絮凝工艺处理低温低浊水时,絮凝区流场流态的变化以及水中浊度、CODMn、UV254的最优去除效果,采用CFD数值模拟探究不同流量(絮凝时间)下絮凝区流场流态,确定最佳絮凝时间;应用响应面中Box-Behnken的中心组合设计方法,研究了流量、混凝剂投加量与涡流反应器投配比及其交互作用对微涡流絮凝工艺去除浊度...     

Scale formation in NF/RO: mechanism and control.

Scale formation of soluble salts is one of the major factors limiting the application of nanofiltration (NF) and reverse osmosis (RO) membranes. This article reviews the scale formation mechanisms in membrane systems, methods to retard scale formation, and a new hybrid system consisting of MF-NF/RO. Two distinct mechanisms in NF/RO fouling by scale formation including surface and bulk crystallization have been identified and investigated. The hydrodynamic operating conditions as well as module geometry determines which fouling mechanism is dominant. An increase in solute concentration at the membrane surface by concentration polarization is responsible for surface crystallization. Conventional methods for scale control only retard the rate of scale formation and their performances are unpredictable. On the other hand, using a MF-NF/RO hybrid system for continuous removal of crystal particles from the retentate stream appears to be effective at high recovery of permeate. When applying the MF-NF/RO hybrid system, substantial improvement in flux is observed in spiral wound module, whereas it is negligible in case of the tubular module. This is because the microfilter could only removes crystals formed in the retentate through the bulk crystallization that is the dominant fouling mechanism in the spiral wound module.     

Membrane filtration for tertiary treatment of biologically treated effluents from the pulp and paper industry.

Discharge waters from activated sludge processes in the pulp and paper industry and from a municipal wastewater treatment plant were filtered with various nanofiltration (NF) and low pressure reverse osmosis (RO) membranes. The purpose was to study flux, retention, and permeate quality after membrane filtration by using a high shear (CR-250/2) filter. The suitability of the achieved permeates for reuse at the industrial site is also discussed. The NF permeate was practically free from colour and organic compounds but contained significant amount of inorganic compounds e.g. chloride ions, especially when a high amount of sulphate containing discharge waters were filtered, in which case a low pressure RO membrane was needed to successfully remove monovalent anions. Organic compounds were almost completely retained by NF and RO membranes and organic carbon in the permeate was less than 10 mg/dm3 on average. The achieved permeate can easily be reused in paper production. Nanofiltration has a significantly higher flux and also a lower fouling tendency than reverse osmosis but it passes through monovalent ions when there is a high sulphate concentration in the water. Therefore, RO might be needed in such cases to produce excellent process water.